Reactions of palladium chloride with amino spirocyclic cyclotriphosphazenes: Isolation and Crystal Structures of Novel Mono- and Bimetallic Complexes Formed by the Hydrolysis of a .lambda.5-Diazaphospholane Ring

Chandrasekaran, A and Krishnamurthy, SS and Nethaji, M (1994) Reactions of palladium chloride with amino spirocyclic cyclotriphosphazenes: Isolation and Crystal Structures of Novel Mono- and Bimetallic Complexes Formed by the Hydrolysis of a .lambda.5-Diazaphospholane Ring. In: Inorganic Chemistry, 33 (14). pp. 3085-3090.

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Abstract

The reaction of the amino spirocyclic cyclotriphosphazene N3P3(NMe2)4(NHCH2CH2CH2NH) (2) with palladium chloride gives the stable chelate complex [PdCl2.2] (4). An X-ray crystallographic study reveals that one of the nitrogen atoms of the diaminoalkane moiety and an adjacent phosphazene ring nitrogen atom are bonded to the metal. An analogous reaction with the phosphazene N3P3(NMe2)4(NHCH2CH2NH) (1) gives initially a similar complex which undergoes facile hydrolysis to give the novel monometallic and bimetallic complexes [PdCl2.HN3P3(O)(NMe2)4(NHCH2CH2NH2)] (5) and [PdCl{N3P3(NMe2)4(NCH2CH2NH2)}]2(O) (6), which have been structurally characterized; in the former, an (oxophosphazadienyl)ethylenediamine is chelated to the metal whereas, in the latter, an oxobridged bis(cyclotriphosphazene) acts as a hexadentate nitrogen donor ligand in its dianionic form. Crystal data for 4 : a = 14.137(1) angstrom, b = 8.3332(5) angstrom, c = 19.205(2) angstrom, beta = 96.108(7)degrees, P2(1)/c, Z = 4, R = 0.027 with 3090 reflections (F > 5sigma(F)). Crystal data for 5 : a = 8.368(2) angstrom, b = 16.841(4) A, c = 16.092(5) angstrom, beta = 98.31(2)degrees, P2(1)/n, Z = 4, R = 0.049 with 3519 reflections (F > 5sigma(F)). Crystal data for 6 : a = 22.455(6) angstrom, b = 14.882(3) angstrom, c = 13.026(5) angstrom, 6 = 98.55(2)degrees, C2/c, Z = 4, R = 0.038 with 3023 reflections (F > 5sigma(F)).

Item Type:	Journal Article
Publication:	Inorganic Chemistry
Publisher:	American chemical society
Additional Information:	Copyright of this article belongs to American chemical society.
Department/Centre:	Division of Chemical Sciences > Inorganic & Physical Chemistry
Date Deposited:	13 Apr 2011 07:25
Last Modified:	13 Apr 2011 07:25
URI:	http://eprints.iisc.ac.in/id/eprint/36840

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