Toggle Main Menu Toggle Search

Open Access padlockePrints

Diverse evolution of [{Ph2P(CH2)(n)PPh2}Pt(mu-S)(2)Pt{Ph2P(CH2)(n)PPh2}] (n=2, 3) metalloligands in CH2Cl2

Lookup NU author(s): Paul Anthony Champkin, Professor William Clegg

Downloads

Full text for this publication is not currently held within this repository. Alternative links are provided below where available.


Abstract

The nucleophilicity of the {Pt2S2} core in [{Ph2P(CH2)(n)PPh2}Pt(mu-S)(2)Pt{Ph2P(CH2)(n)PPh2}] (n = 3, dppp (1); n = 2, dppe (2)) metalloligands toward the CH2Cl2 Solvent has been thoroughly studied. Complex 1, which has been obtained and characterized by X-ray diffraction, is structurally related to 2 and consists of dinuclear molecules with a hinged {Pt2S2} central ring. The reaction of 1 and 2 with CH2Cl2 has been followed by means of P-31, H-1, and C-13 NMR, electrospray ionization mass spectrometry, and X-ray data. Although both reactions proceed at different rates, the first steps are common and lead to a mixture of the corresponding mononuclear complexes [Pt{Ph2P(CH2)(n)PPh2}(S2CH2)], n = 3 (7), 2 (8), and [Pt{Ph2P(CH2)(n)PPh2}Cl-2], n = 3 (9), 2 (10). Theoretical calculations give support to the proposed pathway for the disintegration process of the {Pt2S2} ring. Only in the case of 1, the reaction proceeds further yielding [Pt-2(dppp)(2){mu-(SCH2SCH2S)-S'S}]Cl-2 (11). To confirm the sequence of the reactions leading from 1 and 2 to the final products 9 and 11 or 8 and 10, respectively, complexes 7, 8, and 11 have been synthesized and structurally characterized. Additional experiments have allowed elucidation of the reaction mechanism involved from 7 to 11, and thus, the origin of the CH2 groups that participate in the expansion of the (SCH2S)(2-) ligand in 7 to afford the bridging (SCH2SCH2 S)(2-) ligand in 11 has been established. The X-ray structure of 11 is totally unprecedented and consists of a hinged {(dppp)Pt(mu-S)(2)Pt(dppp)} core capped by a CH2SCH2 fragment.


Publication metadata

Author(s): Mas-Balleste R, Capdevila M, Champkin PA, Clegg W, Coxall RA, Lledos A, Megret C, Gonzalez-Duarte P

Publication type: Article

Publication status: Published

Journal: Inorganic Chemistry

Year: 2002

Volume: 41

Issue: 12

Pages: 3218-3229

ISSN (print): 0020-1669

ISSN (electronic):

Publisher: American Chemical Society

URL: http://dx.doi.org/10.1021/ic0107173

DOI: 10.1021/ic0107173


Altmetrics

Altmetrics provided by Altmetric


Share