Synthesis, Reactivity, and Structural Transformation of Mono- and Binuclear Carboranylamidinate-Based 3d Metal Complexes and Metallacarborane Derivatives
摘要:
A series of carboranylamidinate-based 3d metal complexes are reported. Treatments of 3d metal dichlorides (CoCl2, NiCl2(DME), CuCl2) with the lithium salts of carboranylamidines (Cab(N)H) generate the mononuclear C,N-coordinated complexes [(RN=C(closo-1,2-C2B10H10)-(NHR)](2)M (1-6; M = Co, Ni, Cu; R = iPr, Cy) in moderate yields, respectively. These complexes have similar structures in the solid state, in which the metal atom is coordinated to two nitrogen atoms and bonded to two cage carbon atoms in a distorted-tetrahedral geometry. As a noninnocent ligand, Cab(N)H can be modified to produce carboranylamidinate thiol (Cab(N)SH) and nido derivatives Dcab(N)H (9, 10), respectively. Reaction of cupric acetate with 1 equiv of CabNSH gave the binuclear complexes {[RN=C(closo-1,2-C2B10H10)(NHR)]SCu}(2) (R = iPr (7), Cy (8)) in 66 and 63% yields, respectively. The structure of 7 shows the formation of a Cu-Cu bond, and the geometry of the Cu2S2 core is planar. The zwitterionic nickel dicarbollide complexes (Dcab(N))Ni(PPh3)Cl (11, 12) were prepared by reactions of the lithium salts of Dcab(N)H (9, 10) with NiCl2(PPh3)(2) in THF. All complexes were characterized by elemental analysis and IR and NMR spectroscopy. The structures of 1, 3-5, 7, and 9-11 were further confirmed by single-crystal X-ray diffraction.
单-和双阴离子碳硼烷酰胺化物很容易直接从邻-碳硼烷(1)一锅法获得。1的原位单硅化反应,然后用N,N'-二异丙基碳二亚胺,i PrN C N i Pr或N,N'-二环己基碳二亚胺CyN C NCy处理,提供了碳硼烷磺酸锂(o -C 2 B 10 H 10 C (NH我PR)(ñ我PR)-κ 2 ç,Ñ)栗(DME)(图2a)和(Ô -C 2乙10 ħ 10 C(NH我CY)(Ñ我CY)-κ 2 Ç,Ñ)的Li(THF)2(图2b)。2a,b的受控水解得到游离的碳硼酰胺基o o -C 2 B 10 H 11 C(NH i R)(N i R)(3a:R = i Pr,3b:R = Cy)。第一dimetalated carboranylamidinates,Ô-C 2 B 10 H 10 C(N i Pr)(N i Pr)Li 2(DME)2(4a)(DME = 1,2-二甲氧基乙烷)和o -C