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Iridium and Rhodium Nitrosyl o ‐Catecholato Metal Complexes
Author(s) -
Ghedini Mauro,
Denti Gianfranco,
Dolcetti Giuliano
Publication year - 1976
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1002/ijch.197600049
Subject(s) - tetracoordinate , chemistry , trigonal bipyramidal molecular geometry , dissociation (chemistry) , iridium , phosphine , rhodium , crystallography , ligand (biochemistry) , stereochemistry , metal , atropisomer , coordination geometry , molecule , crystal structure , planar , organic chemistry , catalysis , hydrogen bond , biochemistry , computer graphics (images) , receptor , computer science
The synthesis and characterization of several novel tetra and pentacoordinate catecholato metal nitrosyl complexes of the type Ir(NO)(1,2‐O 2 C 6 H 3 ‐3 or 4‐R)‐P(C 6 H 5 ) 3 ): 3‐R = iso C 3 H 7 ; 4‐R = COOH, H, CH 3 , ter C 4 H 9 ; and M(NO)(1,2‐O 2 C 6 H 3 ‐4‐R)(P(C 6 H 5 ) 3 ): M = Ir and Rh; R = NO 2 , CHO, COOCH 3 ; M = Rh; R = H; are reported together with their IR spectra. Two different classes of cathecolato complexes are obtained, tetracoordinate and pentacoordinate. The pentacoordinate complexes achieve tetracoordination, in solution, by spontaneous and reversible release of a phosphine molecule. The separation of the crystalline species seems to be determined either by the electron withdrawing or releasing power of the cathecolato ring substituents rather than by the solubility of the single species in our preparative conditions. The possibility for the pentacoordinate complexes to have a packed trigonal bipyramid geometry with axial bent nitrosyl NO − and axial equatorial catechol ligand is supported by the easy phosphine dissociation to form the tetracoordinate, which has been observed both in solution and in field desorption mass spectra measurements. For the tetracoordinate complexes a square planar geometry with linear nitrosyl, NO + , is proposed.