Phosphine, arsine and stibine complexes of manganese(I) carbonyl halides: synthesis, multinuclear NMR spectroscopic studies, redox properties and crystal structures

Pope, Simon J. A. ORCID: https://orcid.org/0000-0001-9110-9711 and Reid, Gillian 1999. Phosphine, arsine and stibine complexes of manganese(I) carbonyl halides: synthesis, multinuclear NMR spectroscopic studies, redox properties and crystal structures. Journal of the Chemical Society. Dalton Transactions 1999 (10) , pp. 1615-1622. 10.1039/a900875f

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Abstract

Reaction of [Mn(CO)5X] (X = Cl or Br) with L–L {L–L = dppm (Ph2PCH2PPh2), dppe (Ph2PCH2CH2PPh2), dppp (Ph2PCH2CH2CH2PPh2), C6H4(PPh2)2-o, C6H4(PH2)2-o, dpae (Ph2AsCH2CH2AsPh2), diars [C6H4(AsMe2)2-o], dpsp (Ph2SbCH2CH2CH2SbPh2) or dmsp (Me2SbCH2CH2CH2SbMe2)} or with two molar equivalents of L (= PPh2H, PCy2H or PPhH2) in refluxing CHCl3 yielded the neutral manganese(I) complexes [MnX(CO)3(L–L)] and [MnX(CO)3L2] as yellow or orange solids. Infrared spectroscopic studies confirmed the fac-tricarbonyl arrangement and 1H, 13C-{1H}, 31P-{1H} and 55Mn NMR spectroscopy have been used to probe the solution behaviour. For a given halide 55Mn NMR spectroscopic studies showed some dependence of δ(55Mn) on halide, chelate ring size, substituent and donor atom. X-Ray crystallographic analyses on [MnCl(CO)3{C6H4(PPh2)2-o}], [MnBr(CO)3(dppe)] and the diprimary phosphine complex [MnCl(CO)3{C6H4(PH2)2-o}]·CH2Cl2 confirmed a fac-tricarbonyl arrangement, with the ditertiary or diprimary phosphine chelating. The structure of [MnBr(CO)3(PPhH2)2] also shows a fac-tricarbonyl arrangement with the primary phosphine ligands mutually cis.

Item Type:	Article
Date Type:	Publication
Status:	Published
Schools:	Chemistry
Subjects:	Q Science > QD Chemistry
Publisher:	Royal Society of Chemistry
ISSN:	0300-9246
Last Modified:	21 Oct 2022 10:53
URI:	https://orca.cardiff.ac.uk/id/eprint/41652

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