Synthesis and structural characterization of the first thermally stable, neutral, and electrophilic phosphinidene complexes of vanadium

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DOIResolve DOI: http://doi.org/10.1021/om100915v
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TypeArticle
Journal titleOrganometallics
Volume30
Issue6
Pages13821388; # of pages: 7
AbstractThe first thermally stable, neutral, electrophilic phosphinidene complexes of vanadium, [CpV(CO)3{η1-P(NR2)}] (R = iPr (3a), Cy (3b)), have been prepared by the reaction of [Na]2[CpV(CO)3] with Cl2PNR2. The molecules 3a and 3b have been characterized by microanalysis, IR, and 1H and 31P{1H} NMR spectroscopy, and for 3a also by single-crystal X-ray diffraction. The structure of 3a exhibits a piano stool geometry closely related to that of CpV(CO)4 with an η1-phosphinidene ligand replacing CO in one of the basal coordination sites of the vanadium atom (V(1)−P(1) = 2.300(2) Å). The reactivity of 3a toward a variety of unsaturated substrates: PhC≡CPh, di-tBu-imidazol-2-ydene, PhN3, and Ph2C═N═N has been examined to probe the electrophilic (or nucleophilic) character of the low-coordinate P(I) site. In all cases reactions occur exclusively at the phosphinidene phosphorus atom, without CO displacement, affording examples of P-coordinated phosphirene [CpV(CO)3{P(NiPr2)CPh═CPh}] (7), abnormal NCN carbene adduct [CpV(CO)3{P(NiPr2)-4-cyclo-C3H2-1,3-(NtBu)2)}] (8), diazaphosphaimine [CpV(CO)3{P(NiPr2)═N−N═CPh2}] (12), and P-coordinated phosphaimine [CpV(CO)3{P(NiPr2)═NPh}] (14) complexes. The η1-phosphaimine complexes 12 and 14 lose carbon monoxide to yield derivatives [CpV(CO)2{P(NiPr2)N−N═CPh2}] (9) and [CpV(CO)2{P(NiPr2)═NPh}] (15), which contain η2-(P,N)-coordinated phosphaimine ligands. An η3-(P,N,N)-bound phosphaimine ligand is present in an isomer of 9, namely, [CpV(CO)2{P(NiPr2)N−N═CPh2}], 13. Complexes 3a, 7, 8, 9, 14, and 15 have been characterized by X-ray crystallography.
Publication date
PublisherAmerican Chemical Society
LanguageEnglish
AffiliationNRC Steacie Institute for Molecular Sciences; National Research Council Canada
Peer reviewedYes
NPARC number19734701
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Record identifierd195f57b-0463-4def-9eb3-fd231dc42649
Record created2012-03-29
Record modified2016-05-09
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