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Reductive carbonylation route to Co(0) and Co(I) carbonyl complexes containing bridging, chelating and cleaved diphosphazanes. Structures of [Co(CO){P(OR)(2)(NHMe)}(2)-{P(O)(OR)(2)}{P(H)(OR ')(2)}] (R = CH2CF3, R ' = CH2CH3), [Co-2(CO)(2){mu-MeN{P(OR)(2)}(2)}(3)] (R = CH2CF3), and [Co(CO)-{eta(2)-MeN{P(OR)(2)}(2)}(2)][CoCl3(OC4H8)] (R = Ph)

Ganesan, Mani and Krishnamurthy, Setharampattu S and Nethaji, Munirathinam (1998) Reductive carbonylation route to Co(0) and Co(I) carbonyl complexes containing bridging, chelating and cleaved diphosphazanes. Structures of [Co(CO){P(OR)(2)(NHMe)}(2)-{P(O)(OR)(2)}{P(H)(OR ')(2)}] (R = CH2CF3, R ' = CH2CH3), [Co-2(CO)(2){mu-MeN{P(OR)(2)}(2)}(3)] (R = CH2CF3), and [Co(CO)-{eta(2)-MeN{P(OR)(2)}(2)}(2)][CoCl3(OC4H8)] (R = Ph). In: Journal of Organometallic Chemistry, 579 (1-2). pp. 248-254.

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Abstract

Reduction of CoCl2 by NaBH4 in ethanol in the presence of MeN{P(OR)2}2 (RCH2CF3 L1) and carbon monoxide at one atmospheric pressure gives an unusual mononuclear complex, [Co(CO){P(OR)2(NHMe)}2{P(O)(OR)2}{P(H)(OR%) CH2CF3, R%CH2CH3) 1 formed by cleavage of a P–N bond and by trans esterification. When the reductive carbonylation is carried out by using Zn as the reducing agent in the presence of the diphosphazanes, MeN{P(OR)2}2 (RCH2CF3 L1; Ph L2), the complexes [Co2(CO)2(m-L1)3] 2, [Co2(CO)4(m-L2)2] 3, and [Co(CO)(h2-L2)2][CoCl3(thf)] 4 are isolated. All the complexes have been characterised by elemental analyses and IR, 1H- and 31P-NMR spectroscopic data. The structures of the complexes 1, 2 and 4 are confirmed by single-crystal X-ray diffraction studies.

Item Type: Journal Article
Additional Information: Copyright of this article belongs to Elsevier Science.
Keywords: Cobalt-diphosphazne-carbonyl complexes;Unusual P–N cleavage; Reductive carbonylation;NMR spectra;X-ray structures.
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 21 Dec 2009 10:48
Last Modified: 19 Sep 2010 05:26
URI: http://eprints.iisc.ernet.in/id/eprint/19117

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