混合过渡金属乙炔化物：通过富碳桥连单元连接的含有多达六种不同过渡金属的配合物的合成与表征。
Mixed-transition-metal acetylides: synthesis and characterization of complexes with up to six different transition metals connected by carbon-rich bridging units.
作者信息
Packheiser Rico, Ecorchard Petra, Rüffer Tobias, Lang Heinrich
机构信息
Fakultät für Naturwissenschaften, Institut für Chemie, Lehrstuhl für Anorganische Chemie, Technische Universität Chemnitz, Strasse der Nationen 62, 09111 Chemnitz, Germany.
出版信息
Chemistry. 2008;14(16):4948-60. doi: 10.1002/chem.200701915.
The synthesis and reaction chemistry of heteromultimetallic transition-metal complexes by linking diverse metal-complex building blocks with multifunctional carbon-rich alkynyl-, benzene-, and bipyridyl-based bridging units is discussed. In context with this background, the preparation of [1-{(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C}-3-{(tBu(2)bpy)(CO)(3)ReC[triple bond]C}-5-(PPh(2))C(6)H(3)] (10) (dppf = 1,1'-bis(diphenylphosphino)ferrocene; tBu(2)bpy = 4,4'-di-tert-butyl-2,2'-bipyridyl; Ph = phenyl) is described; this complex can react further, leading to the successful synthesis of heterometallic complexes of higher nuclearity. Heterotetrametallic transition-metal compounds were formed when 10 was reacted with [{(eta(5)-C(5)Me(5))RhCl(2)}(2)] (18), [(Et(2)S)(2)PtCl(2)] (20) or [(tht)AuC[triple bond]C-bpy] (24) (Me = methyl; Et = ethyl; tht = tetrahydrothiophene; bpy = 2,2'-bipyridyl-5-yl). Complexes [1-{(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C}-3-{(tBu(2)bpy)(CO)(3)ReC[triple bond]C}-5-{PPh(2)RhCl(2)(eta(5)-C(5)Me(5))}C(6)H(3)] (19), [{1-[(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C]-3-[(tBu(2)bpy)(CO)(3)ReC[triple bond]C]-5-(PPh(2))C(6)H(3)}(2)PtCl(2)] (21), and [1-{(eta(2)-dppf)(eta(5)-C(5)H(5))RuC[triple bond]C}-3-{(tBu(2)bpy)(CO)(3)ReC[triple bond]C}-5-{PPh(2)AuC[triple bond]C-bpy}C(6)H(3)] (25) were thereby obtained in good yield. After a prolonged time in solution, complex 25 undergoes a transmetallation reaction to produce [(tBu(2)bpy)(CO)(3)ReC[triple bond]C-bpy] (26). Moreover, the bipyridyl building block in 25 allowed the synthesis of Fe-Ru-Re-Au-Mo- (28) and Fe-Ru-Re-Au-Cu-Ti-based (30) assemblies on addition of [(nbd)Mo(CO)(4)] (27), (nbd = 1,5-norbornadiene), or [{[Ti](mu-sigma,pi-C[triple bond]CSiMe(3))(2)}Cu(N[triple bond]CMe)][PF(6)] (29) ([Ti] = (eta(5)-C(5)H(4)SiMe(3))(2)Ti) to 25. The identities of 5, 6, 8, 10-12, 14-16, 19, 21, 25, 26, 28, and 30 have been confirmed by elemental analysis and IR, (1)H, (13)C{(1)H}, and (31)P{(1)H} NMR spectroscopy. From selected samples ESI-TOF mass spectra were measured. The solid-state structures of 8, 12, 19 and 26 were additionally solved by single-crystal X-ray structure analysis, confirming the structural assignment made from spectroscopy.
本文讨论了通过将不同的金属络合物构建单元与基于富碳炔基、苯和联吡啶的多功能桥连单元相连，合成异多金属过渡金属络合物及其反应化学。在此背景下，描述了[1-{(η²-dppf)(η⁵-C₅H₅)RuC≡C}-3-{(tBu₂bpy)(CO)₃ReC≡C}-5-(PPh₂)C₆H₃] (10)的制备（dppf = 1,1'-双(二苯基膦基)二茂铁；tBu₂bpy = 4,4'-二叔丁基-2,2'-联吡啶；Ph = 苯基）；该络合物可进一步反应，成功合成了更高核数的异金属络合物。当10与[{(η⁵-C₅Me₅)RhCl₂}₂] (18)、[(Et₂S)₂PtCl₂] (20) 或 [(tht)AuC≡C-bpy] (24)（Me = 甲基；Et = 乙基；tht = 四氢噻吩；bpy = 2,2'-联吡啶-5-基）反应时，形成了异四金属过渡金属化合物。从而以良好的产率得到了络合物[1-{(η²-dppf)(η⁵-C₅H₅)RuC≡C}-3-{(tBu₂bpy)(CO)₃ReC≡C}-5-{PPh₂RhCl₂(η⁵-C₅Me₅)}C₆H₃] (19)、[{1-[(η²-dppf)(η⁵-C₅H₅)RuC≡C]-3-[(tBu₂bpy)(CO)₃ReC≡C]-5-(PPh₂)C₆H₃}(2)PtCl₂] (21) 和 [1-{(η²-dppf)(η⁵-C₅H₅)RuC≡C}-3-{(tBu₂bpy)(CO)₃ReC≡C}-5-{PPh₂AuC≡C-bpy}C₆H₃] (25)。在溶液中放置较长时间后，络合物25发生金属转移反应生成[(tBu₂bpy)(CO)₃ReC≡C-bpy] (26)。此外，25中的联吡啶构建单元使得在加入[(nbd)Mo(CO)₄] (27)（nbd = 1,5-降冰片二烯）或[{Ti₂}Cu(N≡CMe)][PF₆] (29)（[Ti] = (η⁵-C₅H₄SiMe₃)₂Ti）到25后，能够合成基于Fe-Ru-Re-Au-Mo- (28) 和Fe-Ru-Re-Au-Cu-Ti的组装体。通过元素分析以及红外光谱、¹H、¹³C{¹H}和³¹P{¹H}核磁共振光谱确定了5、6、8、10 - 12、14 - 16、19、21、25、26、28和30的结构。对选定的样品测量了电喷雾电离飞行时间质谱。此外，通过单晶X射线结构分析确定了8、12、19和26的固态结构，证实了光谱分析得出的结构归属。
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