- Syntheses and crystal structures of mononuclear rhodium hydrido complexes from the reactions of [RH(H)2(PPH3)2(ETOH)2] C1O4 with various nitrogen ligands
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Reactions of the Rh hydrido complex [Rh(H)2(PPh3)2(EtOH)2] ClO4 (1) with nitrogen ligands such as 2-(4-thiazolyl)benzimidazole (tbz), pyridazine (pdz), imidazole (im) and pyrimidine (pmd) in CH2Cl2 afforded various mononuclear Rh hydrido complexes, [Rh(H)2(PPh3)2(tbz)]ClO4 (2), [Rh(H)2(PPh3)2(pdz)2]ClO4 ·2CH2Cl2 (3), [Rh(H)Cl(PPh3)2(pdz)2]ClO4 ·CH2Cl2 (4), [Rh(H)2(PPh3)2(im)2] ClO4·2CH2Cl2 (5), [Rh(H)Cl(PPh3)2(im)2]ClO4 ·CH2Cl2 (6), [Rh(H)2(PPh3)2(pmd)2] ClO4·CH2Cl2 (7) and the Rh non-hydrido complex [RhCl2(pmd)4]ClO4 (8). The Rh complexes 2, 3, 5 and 6 were crystallographically characterized. The formation process was monitored by 1H NMR and UV-Vis spectra. In all the Rh hydrido complexes, the Rh atom is coordinated by two PPh3 ligands in trans-positions and two nitrogen ligands in the cis-positions. The remaining sites are occupied by one or two hydride atoms to form a saturated 18-electron framework in a slightly distorted octahedral geometry. For complex 2 an appreciable inter-molecular π interaction is observed between planes of tbz and PPh3 ligands, while an intra-molecular hydrogen bonding interaction between C-H and Cl atoms is found in complex 6.
- Yu, Xiao-Yan,Maekawa, Masahiko,Morita, Tomonori,Chang, Ho-Chol,Kitagawa, Susumu,Jin, Guo-Xin
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p. 1613 - 1620
(2008/10/08)
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