<?xml version="1.0" encoding="UTF-8"?><!DOCTYPE article  PUBLIC "-//NLM//DTD Journal Publishing DTD v3.0 20080202//EN" "http://dtd.nlm.nih.gov/publishing/3.0/journalpublishing3.dtd"><article xmlns:mml="http://www.w3.org/1998/Math/MathML" xmlns:xlink="http://www.w3.org/1999/xlink" dtd-version="3.0" xml:lang="en" article-type="research article"><front><journal-meta><journal-id journal-id-type="publisher-id">IJOC</journal-id><journal-title-group><journal-title>International Journal of Organic Chemistry</journal-title></journal-title-group><issn pub-type="epub">2161-4687</issn><publisher><publisher-name>Scientific Research Publishing</publisher-name></publisher></journal-meta><article-meta><article-id pub-id-type="doi">10.4236/ijoc.2014.45037</article-id><article-id pub-id-type="publisher-id">IJOC-52837</article-id><article-categories><subj-group subj-group-type="heading"><subject>Articles</subject></subj-group><subj-group subj-group-type="Discipline-v2"><subject>Biomedical&amp;Life Sciences</subject><subject> Chemistry&amp;Materials Science</subject></subj-group></article-categories><title-group><article-title>
 
 
  Synthesis, Spectral and Antimicrobial Studies of Bis (Cyclopentadienyl) Titanium (IV) Bis (O,O’-Dialkyl and Alkylenedithiophosphate) Complexes
 
</article-title></title-group><contrib-group><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>dnan</surname><given-names>A. S. El Khaldy</given-names></name><xref ref-type="aff" rid="aff1"><sup>1</sup></xref></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Florence</surname><given-names>Okafor</given-names></name><xref ref-type="aff" rid="aff2"><sup>2</sup></xref></contrib><contrib contrib-type="author" xlink:type="simple"><name name-style="western"><surname>Alaa</surname><given-names>M. Abu Shanab</given-names></name><xref ref-type="aff" rid="aff3"><sup>3</sup></xref></contrib></contrib-group><aff id="aff1"><addr-line>Department of Physics, Chemistry, and Mathematics, College of Engineering, Technology and Physical 
Sciences, Alabama A&amp;amp;M University, Normal, AL, USA</addr-line></aff><aff id="aff2"><addr-line>Department of Biological &amp;amp; Environmental Sciences, College of Agricultural, Life and Natural Sciences, 
Alabama A&amp;amp;M University, Normal, AL, USA</addr-line></aff><aff id="aff3"><addr-line>Chemistry Department, Al-Aqsa University, Gaza, Palestine</addr-line></aff><pub-date pub-type="epub"><day>26</day><month>12</month><year>2014</year></pub-date><volume>04</volume><issue>05</issue><fpage>339</fpage><lpage>346</lpage><history><date date-type="received"><day>14</day>	<month>October</month>	<year>2014</year></date><date date-type="rev-recd"><day>30</day>	<month>November</month>	<year>2014</year>	</date><date date-type="accepted"><day>15</day>	<month>December</month>	<year>2014</year></date></history><permissions><copyright-statement>&#169; Copyright  2014 by authors and Scientific Research Publishing Inc. </copyright-statement><copyright-year>2014</copyright-year><license><license-p>This work is licensed under the Creative Commons Attribution International License (CC BY). http://creativecommons.org/licenses/by/4.0/</license-p></license></permissions><abstract><p>
 
 
  A new complexes of Cp
  <sub>2</sub>Ti[S
  <sub>2</sub>P(OR)
  <sub>2</sub>]
  <sub>2</sub> (where R = Et, Pr-n, Pr-i, Bu-i and Ph) and Cp
  <sub>2</sub>Ti[S
  <sub>2</sub>POGO]
  <sub>2</sub> (where G = -CH
  <sub>2</sub>CMe
  <sub>2</sub>CH
  <sub>2</sub>-, -CH
  <sub>2</sub>CEt
  <sub>2</sub>CH
  <sub>2</sub>- and -CMe
  <sub>2</sub>CMe
  <sub>2</sub>-) were prepared by the dropwise addition of the appropriate 
  O,
  O’-dialkyl or -alkylenedithiophosphoric acid to biscyclopentadienyl titanium dichloride in 1:2 molar ratio and refluxed in benzene solution. These novel deep red colored complexes were characterized by elemental analyses, molecular weight measurements and spectroscopic techniques (IR., NMR 
  <sup>1</sup>H,
  <sup> 13</sup>C and 
  <sup>31</sup>P NMR). These titanium (IV) dithio complexes have also been screened for their antibacterial activities.
 
</p></abstract><kwd-group><kwd>Titanium (IV) Dialkyl and Alkylenedithiophosphate Complexes</kwd></kwd-group></article-meta></front><body><sec id="s1"><title>1. Introduction</title><p>The synthesis of coordination compounds with sulfur containing ligands has been in the center of interest in chemical research for many years [<xref ref-type="bibr" rid="scirp.52837-ref1">1</xref>] - [<xref ref-type="bibr" rid="scirp.52837-ref6">6</xref>] . A survey of literature on dithiophosphato derivatives of titanium and organotitanium reveals that only simple derivatives (e.g., those containing organic and halo substituents on titanium on addition to the dithiophosphato group) have been described [<xref ref-type="bibr" rid="scirp.52837-ref7">7</xref>] [<xref ref-type="bibr" rid="scirp.52837-ref8">8</xref>] . Derivatives containing other monodentate ligands in addition to dithiophosphate have not been isolated. Dialkyl and alkylenedithiophosphates exhibit a variety of coordination modes of bonding [<xref ref-type="bibr" rid="scirp.52837-ref9">9</xref>] - [<xref ref-type="bibr" rid="scirp.52837-ref12">12</xref>] and their metal complexes have important biochemical, analytical and industrial applications [<xref ref-type="bibr" rid="scirp.52837-ref13">13</xref>] - [<xref ref-type="bibr" rid="scirp.52837-ref17">17</xref>] . The biocidial importance of organophosphorus compounds is well known. The synthesis of organotitanium (IV) dithiophosphate compounds provide model systems of interest because the presence of biologically active organophosphorus and organo titanium moieties in a single molecule could provide new information about the bioactivity of titanium compound. In view of the ready conversion of Ti-Cl bonded into Ti-S bonded compounds, the preparative route chosen for the above compounds was the direct interaction between Biscyclopentadienyl Titanium (IV) dichloride and dialkyl (or alkylene) diothiophosphoric acids. Thus, the reactions of Titanocene with dithiophosphoric acids have been carried out in 1:2 molar ratios under mild condition.</p><p>Before discussing the results of the above reactions, it may be relevant to mention the structural features of the Cp<sub>2</sub>TiCl<sub>2</sub> [<xref ref-type="bibr" rid="scirp.52837-ref18">18</xref>] . Titanocene does not adopt the typical “sandwich” structure like ferrocene due to the 4 ligands around the metal center, but rather takes on a distorted tetrahedral shape [<xref ref-type="bibr" rid="scirp.52837-ref19">19</xref>] . Although its crystal structure has not been determined, its structure has been demonstrated in a number of other organotitanium dithiophosphates. In dilute solution, however, the titanocene structure which is monomeric species containing unidentate dithiophosphates and 4-coordinated titanium atoms.</p></sec><sec id="s2"><title>2. Experimental</title><p>Stringent precautions were taken to exclude moisture. Solvents (benzene, n-hexane) were dried by standard methods. Glycols were distilled before use; Titanocene (Merck) was used as received. Dialkyl and alkylenedithiophosphoric acids were prepared by the reaction of phosphorus pentasulfide and alcohols in a 1:4 ratio, and in a 1:2 ratio with glycols as described in the literature [<xref ref-type="bibr" rid="scirp.52837-ref20">20</xref>] . Sulfur was determined by Messenger’s method as barium sulfate. Titanium was determined titanium oxide (cupferron method). Infrared spectra were recorded as Nujol mulls using CsI cells in the region 4000 - 200 cm<sup>−1</sup> on an FT-IR 8201PC spectrophotometer.</p><p><sup>1</sup>H and <sup>13</sup>C spectra were recorded on a Jeol-FT NMR spectrometer-LA300 and using TMS as the internal reference. <sup>31</sup>P NMR spectra were recorded in CHCl<sub>3</sub> using H<sub>3</sub>PO<sub>4</sub> as an external reference on the same instrument. The following synthetic details for a specific 1:2 reaction represent the procedure used to synthesize all compounds.</p><sec id="s2_1"><title>2.1. Reaction between Biscyclopentadienyl Titanium Dichloride with Dialkyl (OPr-n) and Alkylenedithiophosphoric Acids in 1:2 Molar Ratios</title><p>A benzene (~10 ml) solution of HS<sub>2</sub>P(OPr-n)<sub>2</sub> (0.818 g; 3.82 mmol) was added to benzene (~15 ml) solution of Cp<sub>2</sub>TiCl<sub>2</sub> (0.475 g; 1.91 mmol) dropwise with stirring at room temperature. The reaction mixture was refluxed for ~5 hour, during which the color of the reaction mixture changed from color red to dark red. The excess solvent was removed under reduced pressure and the product washed repeatedly by n-hexane and the desired product was finally dried under reduced pressure.</p></sec><sec id="s2_2"><title>2.2. Antimicrobial Studies</title><p>Bioactivity studies were conducted using three bacterial strains; Escherichia coli, Bacillus cereus, and Pseudomonas aeruginosa as test microorganisms.</p><p>Susceptibility of the microorganisms to the novel chemical compounds was determined using the Agar diffusion method and in accordance with the CLSI (formerly NCCLS) guidelines [<xref ref-type="bibr" rid="scirp.52837-ref21">21</xref>] . This method was used as a qualitative method to determine whether each bacterium is resistant, intermediately resistant or susceptible to the synthesized chemicals. The broth cultures of the microorganisms were first grown until they had an optical density (OD) or absorbance of 0.8 - 1.0 at a 600 nm wavelength. Inoculum of approximately 10<sup>6</sup> colony forming unit (CFU) of each isolate was plated on to the Mueller-Hinton Agar plates to form a confluent or lawn growth. The test chemical (400 ug/ml) or control (70% ethanol, v/v) was applied to sterile disks and placed on the inoculated plates and incubated at 37˚C for 24 h.</p><p>The zones of inhibition/clearance of microbial growth around the disks containing the extracts/control were measured. The zone of inhibition was defined as the shortest distance (in mm) from the outside margin of the initial point of microbial growth. Three replicates were made for each test organism.</p></sec></sec><sec id="s3"><title>3. Results and Discussion</title><p>Biscyclopentadienyl titanium bis (dialkyl and alkylenedithiophosphate) have been synthesized by the reaction of biscyclopentadienyl titanium dichloride (Titanocene) with dialkyl and alkylenedithiophosphoric acids in 1:2 molar ratios in refluxing benzene as in Equations (1) and (2).</p><disp-formula id="scirp.52837-formula486"><label>(1)</label><graphic position="anchor" xlink:href="http://html.scirp.org/file/8-1020346x6.png"  xlink:type="simple"/></disp-formula><p>where R = Et, Pr-n, Pr-i, Bu-i and Ph</p><disp-formula id="scirp.52837-formula487"><label>(2)</label><graphic position="anchor" xlink:href="http://html.scirp.org/file/8-1020346x7.png"  xlink:type="simple"/></disp-formula><p>G = -CH<sub>2</sub>CMe<sub>2</sub>CH<sub>2</sub>-, -CH<sub>2</sub>CEt<sub>2</sub>CH<sub>2</sub>- and -CMe<sub>2</sub>CMe<sub>2</sub>.</p><p>The color of the reaction medium changed from red to deep red color with the progress of reaction. Biscyclopentadienyl titanium bis (dialkyl and alkylenedithiophosphate) derivatives are deep red color solids in open and cyclic chain complexes. All these compounds are soluble in common organic solvents like benzene, dichloromethane and chloroform. The molecular weight of all these products determined by cryoscopic method in benzene indicated the monomeric nature of these products (<xref ref-type="table" rid="table1">Table 1</xref>).</p><sec id="s3_1"><title>3.1. IR Spectra</title><p>IR spectra of biscyclopentadienyl titanium bis (dialkyl and alkylenedithiophosphate), have been recorded in the region 4000 - 400cm<sup>−1</sup> [<xref ref-type="bibr" rid="scirp.52837-ref22">22</xref>] [<xref ref-type="bibr" rid="scirp.52837-ref23">23</xref>] . The band shown by the parent acids in the region 2544 - 2400 cm<sup>−1</sup>, due to SH stretching vibration, are absent for biscyclopentadienyl titanium bis(dialkyl and alkylenedithiophosphate) derivatives, indicating the formation of Ti-S bond with the appearance a new band in the regions 428 - 400 cm<sup>−1</sup> [<xref ref-type="bibr" rid="scirp.52837-ref22">22</xref>] [<xref ref-type="bibr" rid="scirp.52837-ref24">24</xref>] . The bands present in the region 1104.0 - 1014.5 cm<sup>−1</sup> and 937.3 - 800 cm<sup>−1</sup> have been assigned to ν (P)-O-C and νP-O-(C) stretching vibrations respectively. Strong bands in the region 995 - 921.9 cm<sup>−11 </sup>are due to dioxaphospholane and dioxaphosphorinane ring vibrations [<xref ref-type="bibr" rid="scirp.52837-ref25">25</xref>] - [<xref ref-type="bibr" rid="scirp.52837-ref27">27</xref>] . The bands observed present in the region 704.0- 638.0 cm<sup>−11</sup> can be assigned to ν P=S vibrations [<xref ref-type="bibr" rid="scirp.52837-ref28">28</xref>] . The bands in medium intensities in the region 602 - 513.0 cm<sup>−11</sup> may be attributed to vibration of νP-S asymmetric and symmetric vibrations [<xref ref-type="bibr" rid="scirp.52837-ref29">29</xref>] . Details regarding the individual bands have been included in <xref ref-type="table" rid="table2">Table 2</xref>.</p><table-wrap id="table1" ><label><xref ref-type="table" rid="table1">Table 1</xref></label><caption><title> Physical properties and analytical data of biscyclopentadienyl titanium bis (O,O-dialkyl and alkylene dithiophosphate) compounds</title></caption><table><tbody><thead><tr><th align="center" valign="middle" >SI. No.</th><th align="center" valign="middle" >Compounds</th><th align="center" valign="middle" >Physical State</th><th align="center" valign="middle" >M. P. ˚C</th><th align="center" valign="middle" >Mol. Wt. Found/(Calc.)</th><th align="center" valign="middle" >% H Found/(Calc.)</th><th align="center" valign="middle" >%C Found/(Calc.)</th><th align="center" valign="middle" >% S Found/(Calc.)</th><th align="center" valign="middle" >% Ti Found/(Calc.)</th><th align="center" valign="middle" ></th></tr></thead><tr><td align="center" valign="middle" >1</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OEt)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >Deep Red Solid</td><td align="center" valign="middle" >137˚</td><td align="center" valign="middle" >542.22/(548.50)</td><td align="center" valign="middle" >5.54/(5.51)</td><td align="center" valign="middle" >38.99/(39.41)</td><td align="center" valign="middle" >22.43 / (23.38)</td><td align="center" valign="middle"  colspan="2"  >7.10/(8.72)</td></tr><tr><td align="center" valign="middle" >2</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OPr-n)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >Deep Red solid</td><td align="center" valign="middle" >153˚</td><td align="center" valign="middle" >598.54/(604.61)</td><td align="center" valign="middle" >6.38/(6.33)</td><td align="center" valign="middle" >43.8/(43.7)</td><td align="center" valign="middle" >20.88 / (21.21)</td><td align="center" valign="middle"  colspan="2"  >7.80/(7.91)</td></tr><tr><td align="center" valign="middle" >3</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OPr-i)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >Deep Red Solid</td><td align="center" valign="middle" >121˚</td><td align="center" valign="middle" >598.69/(604.61)</td><td align="center" valign="middle" >6.29/(6.33)</td><td align="center" valign="middle" >43.92/(43.70)</td><td align="center" valign="middle" >20.98 / (21.21)</td><td align="center" valign="middle"  colspan="2"  >7.83/(7.91)</td></tr><tr><td align="center" valign="middle" >4</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OBu-i)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >Deep Red Solid</td><td align="center" valign="middle" >195˚</td><td align="center" valign="middle" >659.32/(660.72)</td><td align="center" valign="middle" >7.23/(7.01)</td><td align="center" valign="middle" >47.16/(47.26)</td><td align="center" valign="middle" >18.94 / (19.41)</td><td align="center" valign="middle"  colspan="2"  >6.88/(7.24)</td></tr><tr><td align="center" valign="middle" >5</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OPh)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >Deep Red Solid</td><td align="center" valign="middle" >217˚</td><td align="center" valign="middle" >738.11/(740.67)</td><td align="center" valign="middle" >4.23/(4.08)</td><td align="center" valign="middle" >54.89/(55.13)</td><td align="center" valign="middle" >16.47/ (17.32)</td><td align="center" valign="middle"  colspan="2"  >5.91/(6.46)</td></tr><tr><td align="center" valign="middle" >6</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>POCH<sub>2</sub>CMe<sub>2</sub>CH<sub>2</sub>O]<sub>2</sub></td><td align="center" valign="middle" >Deep Red Solid</td><td align="center" valign="middle" >187˚</td><td align="center" valign="middle" >568.67/(572.52)</td><td align="center" valign="middle" >5.48/(5.28)</td><td align="center" valign="middle" >42.16/(41.95)</td><td align="center" valign="middle" >21.97/ (22.40)</td><td align="center" valign="middle"  colspan="2"  >7.95./(8.36)</td></tr><tr><td align="center" valign="middle" >7</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>POCH<sub>2</sub>CEt<sub>2</sub>CH<sub>2</sub>O]<sub>2</sub></td><td align="center" valign="middle" >Deep Red Solid</td><td align="center" valign="middle" >173˚</td><td align="center" valign="middle" >627.78/(628.63)</td><td align="center" valign="middle" >5.98/(6.09)</td><td align="center" valign="middle" >46.22/(45.85)</td><td align="center" valign="middle" >19.97 / (20.40)</td><td align="center" valign="middle"  colspan="2"  >7.81./(7.61)</td></tr><tr><td align="center" valign="middle" >8</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>POCMe<sub>2</sub>CMe<sub>2</sub>O]<sub>2</sub></td><td align="center" valign="middle" >Deep Red Solid</td><td align="center" valign="middle" >203˚</td><td align="center" valign="middle" >599.43/(600.58)</td><td align="center" valign="middle" >5.98/(5.70)</td><td align="center" valign="middle" >43.62/(43.99)</td><td align="center" valign="middle" >21.41/ (21.36)</td><td align="center" valign="middle"  colspan="2"  >7.60/(7.97)</td></tr></tbody></table></table-wrap><table-wrap id="table2" ><label><xref ref-type="table" rid="table2">Table 2</xref></label><caption><title> IR spectral data (cm<sup>−1</sup>) of biscyclopentadienyl titanium bis (O,O-dialkyl and alkylene dithiophosphate) compounds</title></caption><table><tbody><thead><tr><th align="center" valign="middle" >SI. No.</th><th align="center" valign="middle" >Compounds</th><th align="center" valign="middle" >ν(P)-O-C</th><th align="center" valign="middle" >νP-O-(C)</th><th align="center" valign="middle" >Ring Vibration</th><th align="center" valign="middle" >ν P=S</th><th align="center" valign="middle" >νP-S</th><th align="center" valign="middle" >ν (Ti-S)</th></tr></thead><tr><td align="center" valign="middle" >1</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OEt)<sub>2</sub>]<sub>2 </sub></td><td align="center" valign="middle" >1014.5 s</td><td align="center" valign="middle" >817.8 s</td><td align="center" valign="middle" >--</td><td align="center" valign="middle" >644.2 m</td><td align="center" valign="middle" >530.0 w</td><td align="center" valign="middle" >400.0 m</td></tr><tr><td align="center" valign="middle" >2</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OPr-n)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >1060.0 m</td><td align="center" valign="middle" >827.4 m</td><td align="center" valign="middle" >--</td><td align="center" valign="middle" >655.8 m</td><td align="center" valign="middle" >520.0 m</td><td align="center" valign="middle" >408.0 w</td></tr><tr><td align="center" valign="middle" >3</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OPr-i)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >1022.2 m</td><td align="center" valign="middle" >800.4 m</td><td align="center" valign="middle" >--</td><td align="center" valign="middle" >638.0 m</td><td align="center" valign="middle" >540.0 w</td><td align="center" valign="middle" >400.0 m</td></tr><tr><td align="center" valign="middle" >4</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OBu-i)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >1018.3 s</td><td align="center" valign="middle" >804.3 s</td><td align="center" valign="middle" >--</td><td align="center" valign="middle" >661.5 m</td><td align="center" valign="middle" >550.0 m</td><td align="center" valign="middle" >406.0 w</td></tr><tr><td align="center" valign="middle" >5</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OPh)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >1104.0 s</td><td align="center" valign="middle" >820.8 s</td><td align="center" valign="middle" >--</td><td align="center" valign="middle" >682.5 s</td><td align="center" valign="middle" >513.0 w</td><td align="center" valign="middle" >409.0 w</td></tr><tr><td align="center" valign="middle" >6</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>POCH<sub>2</sub>CMe<sub>2</sub>CH<sub>2</sub>O]<sub>2</sub></td><td align="center" valign="middle" >10415 s</td><td align="center" valign="middle" >815.8 m</td><td align="center" valign="middle" >987.5 s</td><td align="center" valign="middle" >667.3 m</td><td align="center" valign="middle" >601.7 m</td><td align="center" valign="middle" >410.0 w</td></tr><tr><td align="center" valign="middle" >7</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>POCH<sub>2</sub>CEt<sub>2</sub>CH<sub>2</sub>O]<sub>2</sub></td><td align="center" valign="middle" >1066.6 s</td><td align="center" valign="middle" >937.3 m</td><td align="center" valign="middle" >995.0 s</td><td align="center" valign="middle" >671.2 m</td><td align="center" valign="middle" >602.0 m</td><td align="center" valign="middle" >428 0 m</td></tr><tr><td align="center" valign="middle" >8</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>POCMe<sub>2</sub>CMe<sub>2</sub>O]<sub>2</sub></td><td align="center" valign="middle" >1022.5 s</td><td align="center" valign="middle" >800.4 s</td><td align="center" valign="middle" >921.9 m</td><td align="center" valign="middle" >704.0 m</td><td align="center" valign="middle" >584.4 m</td><td align="center" valign="middle" >414.0 m</td></tr></tbody></table></table-wrap><p>s = strong, m = medium, w = weak and b = broad absorption band.</p></sec><sec id="s3_2"><title>3.2. <sup>1</sup>H NMR Spectra</title><p>The <sup>1</sup>H NMR spectra Biscyclopentadienyl titanium bis (dialkyl and alkylenedithiophosphate) recorded in CDCl<sub>3</sub>, show the characteristic resonance due to alkoxy and glycoxy (dithio moiety) protons. These <sup>1</sup>H NMR spectral data are given in <xref ref-type="table" rid="table3">Table 3</xref>. The singlet peak at (3.1 - 3.5 ppm) in the parent dithiophosphoric acids and assigned to SH proton, is absent from the spectra of Titanium bis (dithiophosphate) derivatives indicating deprotonation of SH group and forming of Ti -S bond [<xref ref-type="bibr" rid="scirp.52837-ref30">30</xref>] .</p></sec><sec id="s3_3"><title>3.3. <sup>13</sup>C NMR Spectra</title><p>The <sup>13</sup>C NMR spectra of biscyclopentadienyl titanium bis (dialkyl and alkylenedithiophosphate) complexes were recorded in deuterated chloroform at ambient temperature (<xref ref-type="table" rid="table4">Table 4</xref>). The spectra show very small chemical shifts when compared to those obtained for the parent dithiophosphoric acids and indicate no substantial difference in the structure [<xref ref-type="bibr" rid="scirp.52837-ref31">31</xref>] .</p></sec><sec id="s3_4"><title>3.4. <sup>31</sup>P NMR Spectra</title><p>The proton decoupled <sup>31</sup>P NMR spectra of biscyclopentadienyl titanium (IV) bis (dialkyl and alkylenedithiophosphate) derivatives, <xref ref-type="table" rid="table3">Table 3</xref>, show only one signal peak for each complex in the region 77.9 - 93.7 ppm. The observation of only one sharp singlet for all compounds reflects the equivalent nature of phosphorous nuclei and the purity of the compound. However, no notable difference was observed in comparison to the parent acids [<xref ref-type="bibr" rid="scirp.52837-ref32">32</xref>] [<xref ref-type="bibr" rid="scirp.52837-ref33">33</xref>] . According to Glidewell, these small shifts indicate monodentate behavior of the ligand [<xref ref-type="bibr" rid="scirp.52837-ref34">34</xref>] .</p></sec><sec id="s3_5"><title>3.5. Structural Elucidation</title><p>Considering the normal mode of bonding of dithiophosphate with the metal as bidentate chelating ligand and based on the above spectral studies of the complexes using IR, NMR (<sup>1</sup>H, <sup>13</sup>C, <sup>13</sup>P), molecular weight determination and elemental analyses. We suggest the following structure (<xref ref-type="fig" rid="fig1">Figure 1</xref> and <xref ref-type="fig" rid="fig2">Figure 2</xref>).</p></sec><sec id="s3_6"><title>3.6. Results of Bioactivity Tests</title><p>The preliminary results show that the chemical compounds slightly inhibited the growth of Escherich coli and Bacillus cereus after a 24 h incubation period, but had little or no effect on Pseudomonas aeruginosa under similar conditions. See (<xref ref-type="table" rid="table5">Table 5</xref>) and <xref ref-type="fig" rid="fig3">Figure 3</xref>. The results are means of three replicate experiments. Escherichia coli a Gram-negative bacterium commonly found in the lower intestine of warm-blooded organisms [<xref ref-type="bibr" rid="scirp.52837-ref35">35</xref>] appeared to be the most susceptible to all chemicals tested with zones of inhibition ranging from 5.0 &#177; 0.76 (Cp<sub>2</sub>Ti [S<sub>2</sub>P(OPr-n)<sub>2</sub>]<sub>2</sub>) to 11.1 &#177; 0.54 for (Cp<sub>2</sub>Ti [S<sub>2</sub>P(OEt)<sub>2</sub>]<sub>2</sub>). The test chemicals had very little inhibitory effect on Pseudomonas aeruginosa.</p><fig id="fig1"  position="float"><label><xref ref-type="fig" rid="fig1">Figure 1</xref></label><caption><title> Suggested structure for biscyclopentadienyl titanium bis (dialkyldithiophosphate) derivatives</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/8-1020346x8.png"/></fig><fig id="fig2"  position="float"><label><xref ref-type="fig" rid="fig2">Figure 2</xref></label><caption><title> Suggested structure for biscyclopentadienyl titanium bis (alkylenedithiophosphate) derivatives</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/8-1020346x9.png"/></fig><table-wrap id="table3" ><label><xref ref-type="table" rid="table3">Table 3</xref></label><caption><title> <sup>1</sup>H and <sup>31</sup>P NMR spectral data of biscyclopentadienyl titanium bis (O,O-dialkyl and alkylene dithiophosphate) compounds</title></caption><table><tbody><thead><tr><th align="center" valign="middle" >SI. No.</th><th align="center" valign="middle" >Compounds</th><th align="center" valign="middle" ><sup>1</sup>H chemical shift in δ ppm in CDCl<sub>3</sub></th><th align="center" valign="middle" ><sup>31</sup>P chemical (parent acid)</th></tr></thead><tr><td align="center" valign="middle" >1</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OEt)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >1.14, t (J = 6.5 Hz), 12H(CH<sub>3</sub>), 3.7, q (J = 6.0 Hz), 8H(OCH<sub>2</sub>) 6.42, s, 10H(C<sub>5</sub>H<sub>5</sub>)</td><td align="center" valign="middle" >86.0. (85.7)</td></tr><tr><td align="center" valign="middle" >2</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OPr-n)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >0.76, t (J = 7.5 Hz), 12H(CH<sub>3</sub>) 1.34, m (J = 6.5 Hz), 8H(CH<sub>2</sub>) 4.0 - 4.1, t (J = 7.5 Hz, 8H(OCH<sub>2</sub>) 6.6, s, 10H(C<sub>5</sub>H<sub>5</sub>)</td><td align="center" valign="middle" >86.2 (86.1)</td></tr><tr><td align="center" valign="middle" >3</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OPr-i)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >1.21, d (J = 6.6 Hz), 24H(CH<sub>3</sub>) 4.40 - 4.42, m J (PH) = 12 Hz, 4H(OCH) 6.42, s, 10H(C<sub>5</sub>H<sub>5</sub>)</td><td align="center" valign="middle" >82.3 (82.3)</td></tr><tr><td align="center" valign="middle" >4</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OBu-i)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >0.8, d (J = 7 Hz), 24H(CH<sub>3</sub>) 1.92, m (J = 6.5 Hz), 4H(CH) 3.80, d (J = 7 Hz), 8H(OCH<sub>2</sub>) 6.60, s, 10H(C<sub>5</sub>H<sub>5</sub>)</td><td align="center" valign="middle" >85.6 (85.7)</td></tr><tr><td align="center" valign="middle" >5</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OPh)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >7.2 - 7.4, m, 2OH(OC<sub>6</sub>H<sub>5</sub>) 6.4, s, 10H(C<sub>5</sub>H<sub>5 </sub>)<sub> </sub></td><td align="center" valign="middle" >79.9 (79.9)</td></tr><tr><td align="center" valign="middle" >6</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>POCH<sub>2</sub>CMe<sub>2</sub>CH<sub>2</sub>O]<sub>2</sub></td><td align="center" valign="middle" >0.82, s, 12H(CH<sub>3</sub>) 4.10, d, 8H(OCH<sub>2</sub>), J(PH) = 15.6 Hz 6.35, s, 10H(C<sub>5</sub>H<sub>5</sub>)</td><td align="center" valign="middle" >77.4 (77.3)</td></tr><tr><td align="center" valign="middle" >7</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>POCH<sub>2</sub>CEt<sub>2</sub>CH<sub>2</sub>O]<sub>2</sub></td><td align="center" valign="middle" >0.71, t (J = 7.5 Hz), 12H(CH<sub>3</sub>) 1.11, q (J = 7.5 Hz), 8H(CH<sub>2</sub>) 4.02, d, 8H(OCH<sub>2</sub>), J(PH) = 16 Hz 6.28, s, 10H(C<sub>5</sub>H<sub>5</sub>)</td><td align="center" valign="middle" >78.3 (78.5)</td></tr><tr><td align="center" valign="middle" >8</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>POCMe<sub>2</sub>CMe<sub>2</sub>O]<sub>2</sub></td><td align="center" valign="middle" >1.06, s, 24H(CH<sub>3</sub>) 6.50, s, 10H(C<sub>5</sub>H<sub>5</sub>)</td><td align="center" valign="middle" >93.4 (93.1)</td></tr></tbody></table></table-wrap><table-wrap id="table4" ><label><xref ref-type="table" rid="table4">Table 4</xref></label><caption><title> <sup>13</sup>C NMR spectral data of biscyclopentadienyl titanium bis (O,O-dialkyl and alkylene dithiophosphate</title></caption><table><tbody><thead><tr><th align="center" valign="middle"  rowspan="2"  >SI. No.</th><th align="center" valign="middle"  rowspan="2"  >Compound</th><th align="center" valign="middle"  colspan="2"  ><sup> </sup></th><th align="center" valign="middle"  colspan="4"  ><sup>13</sup>C Chemical shift, in ppm</th></tr></thead><tr><td align="center" valign="middle" >CH<sub>3</sub><sup> </sup></td><td align="center" valign="middle" >CH<sub>2</sub><sup> </sup></td><td align="center" valign="middle" >CH<sup> </sup></td><td align="center" valign="middle" >C<sup> </sup></td><td align="center" valign="middle" >CO<sup> </sup></td><td align="center" valign="middle" >C<sub>5</sub>H<sub>5</sub><sup> </sup></td></tr><tr><td align="center" valign="middle" >2</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OPr-n)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >10.0 s</td><td align="center" valign="middle" >23.0 s</td><td align="center" valign="middle" ></td><td align="center" valign="middle" ></td><td align="center" valign="middle" >70.2 s</td><td align="center" valign="middle" >120.4 s</td></tr><tr><td align="center" valign="middle" >4</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OBu-i)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >18.8 s</td><td align="center" valign="middle" >28.5 s</td><td align="center" valign="middle" ></td><td align="center" valign="middle" ></td><td align="center" valign="middle" >74.2 s</td><td align="center" valign="middle" >120.4 s</td></tr><tr><td align="center" valign="middle" >7</td><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>POCH<sub>2</sub>CEt<sub>2</sub>CH<sub>2</sub>O]<sub>2</sub></td><td align="center" valign="middle" >6.8 s</td><td align="center" valign="middle" >22.2 s</td><td align="center" valign="middle" ></td><td align="center" valign="middle" >36.9 s</td><td align="center" valign="middle" >76.2 s</td><td align="center" valign="middle" >120.7 s</td></tr></tbody></table></table-wrap><fig id="fig3"  position="float"><label><xref ref-type="fig" rid="fig3">Figure 3</xref></label><caption><title> Antimicrobial activity of test chemicals</title></caption><graphic mimetype="image"   position="float"  xlink:type="simple"  xlink:href="http://html.scirp.org/file/8-1020346x10.png"/></fig><table-wrap id="table5" ><label><xref ref-type="table" rid="table5">Table 5</xref></label><caption><title> Zones of inhibition (mm) of test chemicals against E. coli, B. cereus and P. aeruginosa</title></caption><table><tbody><thead><tr><th align="center" valign="middle" >TEST chem. compounds</th><th align="center" valign="middle" >Escherichia coli</th><th align="center" valign="middle" >Bacillus cereus</th><th align="center" valign="middle" >Pseudomonas aeruginosa</th></tr></thead><tr><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OEt)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >11.1 &#177; 0.54</td><td align="center" valign="middle" >5.1 &#177; 0.32</td><td align="center" valign="middle" >2.45 &#177; 1.5</td></tr><tr><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OPr-n)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >5.0 &#177; 0.76</td><td align="center" valign="middle" >5.0 &#177; 0.78</td><td align="center" valign="middle" >0.00</td></tr><tr><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OPr-i)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >5.8 &#177; 0.81</td><td align="center" valign="middle" >2.3 &#177; 0.21</td><td align="center" valign="middle" >0.00</td></tr><tr><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OBu-i)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >6.3 &#177; 0.41</td><td align="center" valign="middle" >4.2 &#177; 0.46</td><td align="center" valign="middle" >0.00</td></tr><tr><td align="center" valign="middle" >Cp<sub>2</sub>Ti[S<sub>2</sub>P(OCH<sub>2</sub>C(Et)<sub>2</sub>CH<sub>2</sub>O)<sub>2</sub>]<sub>2</sub></td><td align="center" valign="middle" >6.7 &#177; 0.72</td><td align="center" valign="middle" >3.9 &#177; 0.18</td><td align="center" valign="middle" >2.00 &#177; 3.0</td></tr></tbody></table></table-wrap></sec></sec><sec id="s4"><title>4. Conclusion</title><p>We have successfully synthesized and characterized the new biscyclopentadienyl titanium (IV) bis (O,O dialkyl and alkylenedithiophosphate) compounds. The molecular weight of all these products determined by cryoscopic method in benzene indicated the monomeric nature of these products. The IR, <sup>1</sup>H, <sup>13</sup>C and <sup>31</sup>P NMR spectra and the elemental analysis of all of these titanium complexes are consistent with the proposed tentative structure: (see <xref ref-type="fig" rid="fig1">Figure 1</xref> and <xref ref-type="fig" rid="fig2">Figure 2</xref>). These novel chemical compounds used in this study show monodentate bond with the metal center and antimicrobial activity against E. coli and B. cereus and weak or no effect on P. aeruginosa.</p></sec><sec id="s5"><title>Acknowledgements</title><p>The authors are thankful for financial support from Evans-Allen Federal Appropriated Funds. The authors also wish to express their profound appreciation for the support received from Dr. L. Walker, Prof. Matthew Edwards, Dean Chance M. Glenn, Ms. Dianne Kirnes and Shonda Scott.</p></sec><sec id="s6"><title>NOTES</title></sec></body><back><ref-list><title>References</title><ref id="scirp.52837-ref1"><label>1</label><mixed-citation publication-type="other" xlink:type="simple">Ma, N., Li, Y., Xu, H., Wang, Z. and Zhang, X. (2010) Well-Defined, Reversible Boronate Crosslinked Nanocarriers for Targeted Drug Delivery in Response to pH and cis-Diols. Journal of the American Chemical Society, 132, 442-443.</mixed-citation></ref><ref id="scirp.52837-ref2"><label>2</label><mixed-citation publication-type="other" xlink:type="simple">El khaldy, A.A.S., Abushanab, A.M. and Abu Alkhair, E. (2011) Synthesis and Antimicrobial Studies of Bis (O,O’-Dialkyl and Alkylene Dithiophosphoric Acids) Adducts of Diphenyl Diselenide. 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