Choualeb Aldjia, Braunstein Pierre, Rosé Jacky, Welter Richard
Laboratoire de Chimie de Coordination (UMR 7513 CNRS), Université Louis Pasteur, 4 rue Blaise Pascal, F-67070 Strasbourg Cedex, France.
Inorg Chem. 2004 Jan 12;43(1):57-71. doi: 10.1021/ic034832k.
The tetrahedral cluster RuCo(3)(CO)(12) reacts with various alkynes, including the new PhCtbd1;CC(O)NHCH(2)Ctbd1;CH (L(1)()), to afford the butterfly clusters RuCo(3)(CO)(10)(micro(4)-eta(2)-RC(2)R') (1, R = R' = C(O)OMe; 2, R = H, R' = Ph; 3, R = H, R' = MeC=CH(2); 4, R = H, R' = CH(2)OCH(2)Ctbd1;CH; 5, R = H, R' = CH(2)NHC(O)Ctbd1;CPh), in which the ruthenium atom occupies a hinge position and the alkyne is coordinated in a micro(4)-eta(2) fashion. Reaction of the anions 1-3 with [Cu(NCMe)(4)]BF(4) led to selective loss of the 12e fragment Co(CO)(-) to form [RuCo(2)(CO)(9)(micro(3)-eta(2)-RC(2)R')] (6, R = R' = C(O)OMe; 7, R = H, R' = Ph; 8, R = H, R' = MeC=CH(2)). To prepare functionalized RuCo(3) or FeCo(3) clusters that could be subsequently condensed with a silica matrix via the sol-gel method, we reacted MCo(3)(CO)(12) (M = Ru, Fe) with the alkyne PhCtbd1;CC(O)NH(CH(2))(3)Si(OMe)(3)(L(2)()) and obtained the butterfly clusters MCo(3)(CO)(10)(micro(4)-eta(2)-PhC(2)C(O)NH(CH(2))(3)Si(OMe)(3)) 9 and 10, respectively. Air-stable RuCo(3)(CO)(10)(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3)) (11) was obtained from 1,4-bis(trimethylsilyl)butadiyne and reacted with [Cu(NCMe)(4)]BF(4) to give [RuCo(2)(CO)(9)(micro(3)-eta(2)-HC(2)Ctbd1;CSiMe(3))] (12), owing to partial ligand proto-desilylation, and not the expected [RuCo(2)(CO)(9)(micro(3)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3))]. Reaction of 11 with [NO]BF(4) afforded, in addition to 12, [RuCo(3)(CO)(9)(NO)(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3))] (13) owing to selective CO substitution on a wing-tip cobalt atom with NO. The thermal reaction of 11 with [AuCl(PPh(3))] led to replacement of a CO on Ru by the PPh(3) originating from [AuCl(PPh(3))] and afforded RuCo(3)(CO)(9)(PPh(3))(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;CSiMe(3)) (14), also obtained directly by reaction of 11 with one equivalent of PPh(3). Proto-desilylation of 11 using TBAF/THF-H(2)O afforded RuCo(3)(CO)(10)(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;CH) (15) which, by Sonogashira coupling with 1,4-diiodobenzene, yielded the dicluster complex [RuCo(3)(CO)(10)(micro(4)-eta(2)-Me(3)SiC(2)Ctbd1;C)]C(6)H(4)](2)(-) (16). The crystal structures of NEt(4).3a, NEt(4).4a, 6, NEt(4).11b, NEt(4).14, and [N(n-Bu)(4)].15a have been determined by X-ray diffraction. Preliminary results indicate the potential of silica-tethered alkyne mixed-metal clusters, obtained by the sol-gel method, as precursors to bimetallic particles.
四面体簇合物[RuCo₃(CO)₁₂]⁻与各种炔烃反应，包括新型的PhCtbd1;CC(O)NHCH₂Ctbd1;CH（L(1)⁻），生成蝴蝶状簇合物[RuCo₃(CO)₁₀(μ₄-η²-RC₂R')]⁻（1，R = R' = C(O)OMe；2，R = H，R' = Ph；3，R = H，R' = MeC=CH₂；4，R = H，R' = CH₂OCH₂Ctbd1;CH；5，R = H，R' = CH₂NHC(O)Ctbd1;CPh），其中钌原子占据铰链位置，炔烃以μ₄-η²方式配位。阴离子1 - 3与[Cu(NCMe)₄]BF₄反应导致12e片段Co(CO)⁻选择性损失，形成[RuCo₂(CO)₉(μ₃-η²-RC₂R')]（6，R = R' = C(O)OMe；7，R = H，R' = Ph；8，R = H，R' = MeC=CH₂）。为了制备可通过溶胶 - 凝胶法随后与二氧化硅基质缩合的功能化RuCo₃或FeCo₃簇合物，我们使[MCo₃(CO)₁₂]⁻（M = Ru，Fe）与炔烃PhCtbd1;CC(O)NH(CH₂)₃Si(OMe)₃（L(2)⁻）反应，分别得到蝴蝶状簇合物[MCo₃(CO)₁₀(μ₄-η²-PhC₂C(O)NH(CH₂)₃Si(OMe)₃)]⁻ 9和1十种。由1,4 - 双（三甲基硅基）丁二炔得到空气稳定的[RuCo₃(CO)₁₀(μ₄-η²-Me₃SiC₂Ctbd1;CSiMe₃)]⁻（11），它与[Cu(NCMe)₄]BF₄反应生成[RuCo₂(CO)₉(μ₃-η²-HC₂Ctbd1;CSiMe₃)]（12），这是由于部分配体原脱硅作用，而不是预期的[RuCo₂(CO)₉(μ₃-η²-Me₃SiC₂Ctbd1;CSiMe₃)]。11与[NO]BF₄反应，除了生成12外，还由于在翼尖钴原子上NO选择性取代CO而生成[RuCo₃(CO)₉(NO)(μ₄-η²-Me₃SiC₂Ctbd1;CSiMe₃)]（13）。11与[AuCl(PPh₃)]的热反应导致Ru上的一个CO被源自[AuCl(PPh₃)]的PPh₃取代，生成[RuCo₃(CO)₉(PPh₃)(μ₄-η²-Me₃SiC₂Ctbd1;CSiMe₃)]⁻（14），也可通过11与一当量的PPh₃直接反应得到。使用TBAF/THF - H₂O对11进行原脱硅作用得到[RuCo₃(CO)₁₀(μ₄-η²-Me₃SiC₂Ctbd1;CH)]⁻（15），它通过与1,4 - 二碘苯的Sonogashira偶联反应，生成双簇合物[[RuCo₃(CO)₁₀(μ₄-η²-Me₃SiC₂Ctbd1;C)]₂C₆H₄]²⁻（16）。NEt₄·3a、NEt₄·4a、6、NEt₄·11b、NEt₄·14和[N(n - Bu)₄]·15a的晶体结构已通过X射线衍射测定。初步结果表明，通过溶胶 - 凝胶法获得的二氧化硅连接的炔烃混合金属簇合物作为双金属颗粒前体的潜力。
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