Synthesis and Characterization of m-AlkyneMolybdenum¡Ó and Tungsten¡ÓCobalt Clusterscontaining Functionally SubstitutedCyclopentadienyl Ligands$Li-Cheng Song,* Qing-Mei Hu, Jin-Song Yang and Jin-Yu ShenDepartment of Chemistry, Nankai University, Tianjin 300071, ChinaEight new -alkyne molybdenum¡Ó and tungsten¡Ócobalt clusters containing functionally substituted cyclopentadienylligands have been synthesized via organic carbonyl transformation reactions of clusters [(5-MeCOC5H4)(OC)2M-(-C2Ph2)Co(CO)3] (M Mo or W).Transition-metal clusters, particularly those containingfunctionally substituted cyclopentadienyl ligands are ofgreat interest due to their potential applications in catalyticprocesses1¡Ó4 and for synthesizing a variety of novel clusterderivatives which would be dicult or even not possible byother methods.5,6 Herein we report some transformationreactions of the carbonyl group on the cyclopentadienylring of clusters [(Z5-MeCOC5H4)(OC)2(m-C2Ph2)Co(CO)3](M Mo or W), from which eight new m-alkyne molyb-denum¡Ó and tungsten¡Ócobalt cluster derivatives wereobtained.We found that clusters [(Z5-MeCOC5H4)(OC)2M-(m-C2Ph2)Co(CO)3] (A, M Mo; B, M W) could bereduced by NaBH4 in methanol to give secondary alcoholclusters 1 and 2, whereas they reacted with MeMgI followedby acidic hydrolysis to give tertiary alcohol clusters 3 and 4,respectively.More interestingly, reactions of A and B with2,4-dinitrophenylhydrazine aorded their phenylhydrazonederivatives 5 and 6, whereas when treated with Wittigreagent Ph3P1CH2 they gave corresponding olenic clusterderivatives 7 and 8, respectively.All the reactions mentionedare summarized in Scheme 1.Compounds 1¡Ó8 are all new functional cyclopentadienylMCoC2 clusters (M Mo or W), which have been wellcharacterized by elemental analysis, IR, 1H NMR and MSdata. For example, the IR spectra of 1¡Ó4 show the hydroxylgroup absorption bands at 3400¡Ó3436 cm£¾1; 5¡Ó8 exhibit theabsorption bands characteristic of the functional groupsof C1N at 1614 cm£¾1 and C1C at 1625¡Ó1630 cm£¾1,respectively.The 1H NMR spectra of 1¡Ó8 reveal all thecorresponding protons, such as those of the hydroxylgroups of 1¡Ó4 between d 1.46 and 1.60, the protons of the2,4-dinitrophenyl groups of 5, 6 at d 7.83¡Ó9.20, and thoseattached to the double bond of 7, 8 at d 4.84¡Ó5.13.ExperimentalIR and 1H NMR spectra were recorded on a Nicolet FT-IR 5DXspectrophotometer and a JEOL FX 90Q spectrometer.Analyses(C, H), MS and melting point were determined using a Perkin-Elmer 240C model analyzer, a HP 5988A spectrometer and aYanako MP-500 instrument, respectively. All reactions werecarried out under nitrogen. Commercial NaBH4, Ph3PCH3Br and2,4-dinitrophenylhydrazine were used as received; MeMgI7 and[(Z5-MeCOC5H4)(OC)2M(m-C2Ph2)Co(CO)3] (M Mo or W)8 wereprepared according to literature methods.Preparations.Compounds of 1 and 2. A 50 ml two-necked askwas charged with [(5-MeCOC5H4)(OC)2M(-C2Ph2)Co(CO)3] A(58 mg, 0.1 mmol) or [(5-MeCOC5H4)(OC)2W(-C2Ph2)Co(CO)3] B(69 mg, 0.1 mmol), NaBH4 (7.6 mg, 0.2 mmol) and MeOH (3 ml).The mixture was stirred for 1.5 h at r.t.and then subjected toTLC using CH2Cl2 as eluent to give 1 or 2. 1: red oil, yield 76%;~max/cm£¾1 2057, 2000, 1975, 1926 (C2O), 3400 (OH); H (CDCl3)1.40 (d, 3 H, J 7.2, CH3), 1.46¡Ó1.60 (br, 1 H, OH), 4.48 (q, 1 H,J 7.2 Hz, CH), 5.18¡Ó5.54 (m, 4 H, C5H4), 7.10¡Ó7.58 (m, 10 H,2C6H5); m/z 402 (M £¾ 2Ph £¾ CO, 1), 181 (C2CoMo, 3%)(Found: C, 53.74; H, 3.26.C26H19CoMoO6 requires C, 53.63; H,3.29%). 2: red oil, yield 51%; ~max/cm£¾1 2049, 2000, 1975, 1926(C2O), 3435 (OH). H (CDCl3) 1.40 (d, 3 H, J 7.2, CH3), 1.48¡Ó1.60 (br, 1 H, OH), 4.50 (q, 1 H, J 7.2 Hz, CH), 5.20¡Ó5.58 (m, 4 H,C5H4), 7.00¡Ó7.40 (m, 10 H, 2C6H5); m/z 614 (M £¾ 2CO, 8), 267(C2CoW, 5%) (Found: C, 47.08; H, 2.63. C26H19CoO6W requiresC, 46.59; H, 2.86%).Compounds 3 and 4. A 50 ml two-necked ask was chargedsequentially with diethyl ether (10 ml), A (197 mg, 0.34 mmol) or B(227 mg, 0.34 mmol) and MeMgI¡Ódiethyl ether solution (0.59 M,2.0 ml) with stirring at r.t.After stirring for 3 h, distilled water(50 ml) and dilute HCl (0.167 M, 10 ml) were added. The etherphase was separated and the aqueous phase extracted with diethylether (210 ml). All the ether layers were combined. After removalof the ether, the residue was subjected to TLC separation usingCH2Cl2¡Ólight petroleum (bp 60¡Ó90 8C) (2 :1) as eluent to give 3 or4. 3: red oil, yield 12%; ~max/cm£¾1 2049, 2000, 1975, 1934 (C2O),3436 (OH); dH (CDCl3) 1.52 (s, 6 H, 2CH3), 1.40¡Ó1.50 (br, 1 H,OH), 5.14 (t, 2 H, J 2.4, H3, H4), 5.48 (t, 2 H, J 2.4 Hz, H2, H5),7.12¡Ó7.48 (m, 10 H, 2C6H5); m/z 542 (M £¾ 2CO, 0.3), 181(C2CoMo, 0.4%) (Found: C, 54.80; H, 3.62. C27H21CoMoO6requires C, 54.38; H, 3.55%). 4: red oil, yield 15%; ~max/cm£¾1 2049,2000, 1975, 1926 (C2O), 3403 (OH); dH (CDCl3) 1.54 (s, 6 H,2CH3), 1.46¡Ó1.56 (br, 1 H, OH), 5.32 (t, 2 H, J 2.4, H3, H4), 5.52(t, 2 H, J 2.4 Hz, H2, H5), 7.28 (s, 10 H, 2C6H5); m/z 628J.Chem. Research (S),1998, 344¡Ó345$Scheme 1$This is a Short Paper as dened in the Instructions for Authors,Section 5.0 [see J. Chem. Research (S), 1998, Issue 1]; there is there-fore no corresponding material in J. Chem. Research (M).*To receive any correspondence.344 J. CHEM. RESEARCH (S), 1998(M £¾ 2CO, 0.5), 267 (C2CoW, 3%) (Found: C, 49.09; H, 3.02.C27H21CoO6W requires C, 47.40; H, 3.09%).Compounds 5 and 6. A 50 ml two-necked ask was charged withA (150 mg, 0.26 mmol) or B (400 mg, 0.26 mmol) and anhydrousethanol (5 ml), to which was slowly added a 2,4-dinitrophenylhydra-zine solution (1.5 ml, 0.52 mmol) (prepared by dissolving 1.0 g of2,4-dinitrophenylhydrazine in 5 ml of 98% H2SO4, 10ml of H2Oand 35 ml of 95% C2H5OH) with stirring.After stirring at r.t. for1.5 h to give a precipitate, which was puried by TLC usingCH2Cl2¡Ólight petroleum¡Ódiethyl ether (1:5:1) as eluent to aord 5or 6. 5: brown-red solid, mp 95 8C (decomp.), yield 41%; ~max/cm£¾12049, 1983, 1942 (C2O), 1614 (C1N); dH (CDCl3) 1.72 (s, 3 H,CH3), 5.52 (s, 2 H, H3, H4 of C5H4 ring), 5.76 (s, 2 H, H2, H5of C5H4 ring), 7.20 (s, 10 H, 2C6H5). 7.83 (d, 1 H, J 9.8, H6 ofbenzene ring), 8.30 (d, 1 H, J 9.8 Hz, H5 of benzene ring), 9.20(s, 1 H, H3 of benzene ring), 10.88 (s, 1 H, NH) (Found: C, 51.00;H, 3.29; N, 7.58. C32H21CoMoN4O9 requires C, 50.54; H, 2.78;N, 7.37%). 6: brown-red solid, mp 128 8C (decomp.), yield 72%;~max/cm£¾1 2049, 2000, 1975, 1934 (C2O), 1614 (C1N); dH(CDCl3) 1.70 (s, 3 H, CH3), 5.62 (t, 2 H, J 2.5, H3, H4 of C5H4ring), 5.82 (t, 2 H, J 2.5, H2 H5 of C5H4 ring), 7.21 (s, 10 H,2C6H5) 7.85 (d, 1 H, J 9.7, H6 of benzene ring), 8.36 (d, 1 H, J9.7 Hz, H5 of benzene ring), 9.18 (s, 1 H, H3 of benzene ring), 10.91(s, 1 H, NH) (Found: C, 45.13; H, 2.60; N, 6.85.C32H21CoN4O9Wrequires.C, 45.31; H, 2.50; N, 6.61%).Compounds 7 and 8. A 50 ml two-necked ask was chargedwith Ph3PCH3Br (528 mg, 1.48 mmol) and THF (20 ml), to whichwas slowly added a BunLi¡Óhexane solution (1.06 M, 1.4 ml) at 0 8Cand then stirred for 4 h at r.t. to give a mixture containing Wittigreagent Ph3P1CH2. To this was added 10 ml of a THF solutionof A (429 mg, 0.74 mmol) or B (494 mg, 0.74 mmol) and then themixture was stirred for 3 h at r.t. It was subjected to TLC usingCH2Cl2¡Ólight petroleum (1: 3) as eluent to give 7 or 8. 7: red solid,mp 56¡Ó57 8C, yield 43%; ~max/cm£¾1 2041, 2007, 1975, 1934 (C2O),1625 (C1C); dH (CDCl3) 1.76 (s, 3 H, CH3), 4.84 (s, 1 H, C1CH),5.13 (s, 1 H, C1CH), 5.20 (s, 2 H, H3, H4), 5.48 (s, 2 H, H2, H5),7.23 (s, 10 H, 2C6H5); m/z 524 (M £¾ 2CO, 7%) (Found: C, 56.88;H, 3.60. C27H19CoMoO5 requires C, 56.94; H, 3.54%). 8: red solid,mp 78¡Ó80 8C, yield 23%; ~max/cm£¾1 2041, 2000, 1975, 1942 (C2O),1631 (C1C); dH (CDCl3) 1.72 (s, 3 H, CH3), 4.86 (s, 1 H, C1CH),5.10 (s, 1 H, C1CH), 5.30 (s, 2 H, H3, H4), 5.52 (s, 2 H, H2, H5),7.18 (s, 10 H, 2C6H5); m/z 610 (M £¾ 2CO, 9%) (Found: C, 48.95;H, 3.10.C27H19CoO5W requires C, 48.68; H, 2.87%).We thank the National Natural Science Foundation ofChina, the Laboratory of Organometallic Chemistry and theSpecial Foundation of State Education Committee of Chinafor nancial support.Received, 13th January 1998; Accepted, 2nd March 1998Paper E/8/00350EReferences1 E. L. 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