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Reactions of $Cu_3(dppm)_3(\mu_3-OH)(ClO_4)_2$ (dppm=bis-(diphenylphosphino) methane) with Soft Heterocumulenes

Sivasankar, C and Bera, JK and Nethaji, M and Samuelson, AG (2004) Reactions of $Cu_3(dppm)_3(\mu_3-OH)(ClO_4)_2$ (dppm=bis-(diphenylphosphino) methane) with Soft Heterocumulenes. In: Journal of Organometallic Chemistry, 689 (16). pp. 2726-2732.

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Abstract

The reaction of $[Cu_3(dppm)_3(\mu_3-OH)](ClO_4)_2$ (1) with heterocumulenes (X‚C‚S; X=NPh, NMe and S) has been studied. The $\mu_3-OH$ ligand inserts into PhNCS and MeNCS only in the presence of methanol. Insertion products are formed in accord with earlier observations made with copper(I)–aryloxides. On heating, the insertion products convert to a S bridged cluster $[Cu_4(dppm)_4(\mu_4- S)](ClO_4)_2$ (8), having a tetrameric core. However, in the reaction with $CS_2$, 1 is converted to 8 even at room temperature in the presence of methanol. On the other hand, the dimeric complex $[Cu_2(dppm)_2(CH_3CN)_4](ClO_4)_2$, reacts with $CS_2$ to give (diphenylphosphinomethyl)- diphenylphosphine sulfide, $Ph_2P–CH_2–P(=S)Ph_2$ (dppmS), which forms the complex $[Cu(dppmS)_2]ClO_4$ (9). A single crystal X-ray crystallographic study of 9, the .rst copper(I) complex of dppmS has been taken up to con.rm the mono-oxidation of the dppm ligand and the nuclearity of the complex. Reactions of complex 1 with heterocumulenes and with elemental sulfur, are compared.

Item Type: Journal Article
Additional Information: The copyright belongs to Elsevier.
Keywords: Heterocumulenes reactions;Cu(I)-dppm;Ligand oxidation;dppmS;Copper(I);Insertion reaction
Department/Centre: Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited: 19 Apr 2006
Last Modified: 19 Sep 2010 04:25
URI: http://eprints.iisc.ernet.in/id/eprint/6364

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