Synthesis and structures of rhodium isocyanide complexes containing an. eta. sup 2 -hydrotris(3,5-dimethylpyrazolyl)borate ligand

Journal Article · Wed Feb 20 04:00:00 EST 1991 · Inorganic Chemistry; (United States)

DOI:https://doi.org/10.1021/ic00004a031· OSTI ID:6020675

Jones, W D; Hessell, E T ^[1]

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1. Univ. of Rochester, NY (United States)

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.

• DOE Contract Number: FG02-86ER13569
• OSTI ID: 6020675
• Journal Information: Inorganic Chemistry; (United States), Journal Name: Inorganic Chemistry; (United States) Journal Issue: 4 Vol. 30:4; ISSN 0020-1669; ISSN INOCA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKANES
AZOLES
CHEMICAL PREPARATION
CHLORINE COMPOUNDS
COMPLEXES
CRYSTAL STRUCTURE
DATA
ESTERS
EXPERIMENTAL DATA
HALOGEN COMPOUNDS
HETEROCYCLIC COMPOUNDS
HYDROCARBONS
INFORMATION
ISOCYANIC ACID ESTERS
MOLECULAR STRUCTURE
NUMERICAL DATA
ORGANIC COMPOUNDS
ORGANIC NITROGEN COMPOUNDS
PYRAZOLES
RHODIUM COMPLEXES
SYNTHESIS
TRANSITION ELEMENT COMPLEXES