Synthesis and structures of rhodium isocyanide complexes containing an. eta. sup 2 -hydrotris(3,5-dimethylpyrazolyl)borate ligand
Synthesis and structures of rhodium isocyanide complexes containing an. eta. sup 2 -hydrotris(3,5-dimethylpyrazolyl)borate ligand
复制标题
含异氰化铑配合物的合成和结构。
DOI：
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发表时间：
1991
期刊：
影响因子：
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通讯作者：
E. Hessell
中科院分区：
文献类型：
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作者：
W. Jones;E. Hessell
Complexes of the general type HB(Pz*){sub 3}Rh(CNR){sub 2} (Pz{sup *} = 3,5-dimethylpyrazol-1-yl, R = neopentyl, 2,6-xylyl, methyl) were prepared by reaction of an isocyanide and K(HB(Pz{sup *}){sub 3}) with (RhCl(C{sub 2}H{sub 4}){sub 2}){sub 2} in benzene. The complexes with R = neopentyl (1a) and R = 2,6-xylyl (1b) have been structurally characterized, and the crystal structures are reported. The HB(Pz*){sub 3} ligand in both 1a and 1b is bidentate, with the noncoordinated pyrazole ring lying roughly cofacial with the square plane formed by the metal, two-coordinated isocyanides, and two-coordinated pyrazole rings with HB(Pz*){sub 3}. A comparison of the infrared and NMR spectra of 1a in solution (C{sub 6}D{sub 6}) and the solid state (KBr pellet) with the corresponding solution and solid-state spectra of H{sub 2}B(Pz*){sub 2}Rh(CNR){sub 2} (2) (R = neopentyl) indicates that complex 1a remains square planar in solution and possesses a rapidly fluxional bidentate HB(Pz*){sub 3} ligand. Complex 1a reacts with HBF{sub 4} to give the metal hydride salt (HB(Pz*){sub 3}Rh(H)(CNR){sub 2})BF{sub 4} (3) (R = neopentyl), which has been structurally characterized.
Complexes of the general type HB(Pz*){sub 3}Rh(CNR){sub 2} (Pz{sup *} = 3,5-dimethylpyrazol-1-yl, R = neopentyl, 2,6-xylyl, methyl) were prepared by reaction of an isocyanide and K(HB(Pz{sup *}){sub 3}) with (RhCl(C{sub 2}H{sub 4}){sub 2}){sub 2} in benzene. The complexes with R = neopentyl (1a) and R = 2,6-xylyl (1b) have been structurally characterized, and the crystal structures are reported. The HB(Pz*){sub 3} ligand in both 1a and 1b is bidentate, with the noncoordinated pyrazole ring lying roughly cofacial with the square plane formed by the metal, two-coordinated isocyanides, and two-coordinated pyrazole rings with HB(Pz*){sub 3}. A comparison of the infrared and NMR spectra of 1a in solution (C{sub 6}D{sub 6}) and the solid state (KBr pellet) with the corresponding solution and solid-state spectra of H{sub 2}B(Pz*){sub 2}Rh(CNR){sub 2} (2) (R = neopentyl) indicates that complex 1a remains square planar in solution and possesses a rapidly fluxional bidentate HB(Pz*){sub 3} ligand. Complex 1a reacts with HBF{sub 4} to give the metal hydride salt (HB(Pz*){sub 3}Rh(H)(CNR){sub 2})BF{sub 4} (3) (R = neopentyl), which has been structurally characterized.