کد مقاله کد نشریه سال انتشار مقاله انگلیسی نسخه تمام متن
1339505 979707 2010 8 صفحه PDF دانلود رایگان
عنوان انگلیسی مقاله ISI
Bisphosphine monoxides with o-phenylene backbones in Pt, Pd and Fe complexes
موضوعات مرتبط
مهندسی و علوم پایه شیمی شیمی معدنی
پیش نمایش صفحه اول مقاله
Bisphosphine monoxides with o-phenylene backbones in Pt, Pd and Fe complexes
چکیده انگلیسی

A new route to aromatic bisphosphine monoxides has been explored through ortholithiation of triphenylphosphine oxide and subsequent reaction of the lithiated intermediate with a range of alkyl and aryl phosphine chlorides. Routes to the known bisphosphine monoxide (BMPO) (o-C6H4){P(O)Ph2}PPh2 (2aO) and a range of new BPMOs of the type Ph2P(O)(o-C6H4)PR2 where R2 = iPr2, Cy2, Et2 are described. Reaction of 2aO with MCl2(cod) (M = Pd, Pt; cod = cyclooctadiene) gives products of the form [MCl(κ1-P-2aO)(κ2-P,O-2aO)]+ Cl− and MCl2(κ2-P,O-2aO); the former exhibits fluxional behaviour which has been analysed by 195Pt NMR and 31P variable-temperature NMR spectroscopy. The bidentate complex is not fluxional for either the Pd or the Pt example; the Pt complex PtCl2(κ2-P,O-2aO) has been characterised by X-ray crystallography. By comparison of the product distribution seen by 31P NMR spectroscopy and ESI-MS it was established that the different coordination modes of 2aO result in quite different behaviour of the complexes when studied by ESI-MS; when the O is formally coordinated to the metal its ionisation efficiency is very low. Synthesis of Fe(CO)4(2aO) confirmed the ability of the 2aO ligand to render a neutral complex with no alternative pathways for ionisation to be readily detected by ESI-MS.

Bisphosphine monoxide ligands may be prepared via treatment of ortholithiated triphenylphosphine oxide with a range of alkyl and aryl phosphine chlorides; the resulting hemilabile ligands render the complexes to which they are bound amenable to analysis by electrospray ionisation mass spectrometry when coordinated in κ1 fashion.Figure optionsDownload as PowerPoint slide

ناشر
Database: Elsevier - ScienceDirect (ساینس دایرکت)
Journal: Polyhedron - Volume 29, Issue 1, 13 January 2010, Pages 254–261
نویسندگان
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