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Please use this identifier to cite or link to this item: http://repository.iitr.ac.in/handle/123456789/3538
Title: A new family of acylrhodium organometallics
Authors: Pattanayak S.
Chattopadhyay S.
Ghosh, Kaushik
Ganguly S.
Ghosh P.
Chakravorty A.
Published in: Organometallics
Abstract: The Schiff mono bases of 2,6-diformyl-4-methylphenol, 1, react with RhCl3·3H2O and PPh3 in ethanol, affording dichloro[4-methyl-6-((arylimino)methyl)phenolato-C 1,O]bis(triphenylphosphine)rhodium(III), Rh(XLsb)(PPh3)2Cl2 (5; X = H, Me, OMe, Cl). Organometallics of the type (carboxylato)[4-methyl-6-formylphenolato-C 1,O]bis(triphenylphosphine]rhodium(III), Rh(Lal)(PPh3)2(RCO2) (6; R = H, Me, Et, Ph), have been synthesized by oxidative addition of 1 to RhCl(PPh3)3 in the presence of dilute RCO2H in ethanol. Replacement of RCO2H by dilute HNO3 has afforded the nitrate analogue Rh(Lal)(PPh3)2(NO3) (7). Species of type 5 are susceptible to aldiminium → aldehyde hydrolysis in a dichloromethane-acetone-water mixture with concomitant chloride dissociation, furnishing Rh(Lal)(PPh3)2Cl (8a), from which the N-bonded nitrite Rh(Lal)(PPh3)2(NO2) (8b) has been generated metathetically. The four types of species 5-8 are interconvertible, and a possible reaction pathway involving pentacoordinate intermediates is proposed. The X-ray structures of Rh(MeLsb)(PPh3)2Cl2 (5b; bis(dichloromethane) adduct), Rh(Lal)(PPh3)2(MeCO2) (6b), Rh(Lal)(PPh3)2(NO3) (7), and Rh-(Lal)(PPh3)2(NO2) (8b) have been determined. Among these, 5b, 6b, and 7 are pseudooctahedral - the bonds trans to the acyl function being longer by 0.2-0.4 Ã… compared to those trans to phenolato oxygen. Complex 8b is square pyramidal, there being no ligand trans to the acyl function. In 5b iminium-phenolato (N⋯O, 2.66(1) Ã…) and in the remaining species aldehyde-phenolato (C⋯O, 2.86(1) Ã…) hydrogen bonding is present. Internal charge balance is crucial for the stability of the present organometallics.
Citation: Organometallics (1999), 18(8): 1486-1494
URI: https://doi.org/10.1021/om980748e
http://repository.iitr.ac.in/handle/123456789/3538
Issue Date: 1999
Publisher: American Chemical Society
ISSN: 2767333
Author Scopus IDs: 36889142600
7403001884
57204513823
7102863089
7402072902
7005083014
Author Affiliations: Pattanayak, S., Department of Inorganic Chemistry, Indian Assoc. the Cultiv. of Sci., Calcutta 700 032, India
Chattopadhyay, S., Department of Inorganic Chemistry, Indian Assoc. the Cultiv. of Sci., Calcutta 700 032, India
Ghosh, K., Department of Inorganic Chemistry, Indian Assoc. the Cultiv. of Sci., Calcutta 700 032, India
Ganguly, S., Department of Inorganic Chemistry, Indian Assoc. the Cultiv. of Sci., Calcutta 700 032, India
Ghosh, P., Department of Inorganic Chemistry, Indian Assoc. the Cultiv. of Sci., Calcutta 700 032, India
Chakravorty, A., Department of Inorganic Chemistry, Indian Assoc. the Cultiv. of Sci., Calcutta 700 032, India
Corresponding Author: Chakravorty, A.; Department of Inorganic Chemistry, Indian Assoc. the Cultiv. of Sci., Calcutta 700 032, India
Appears in Collections:Journal Publications [CY]

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