Synthesis and Reactivity of a Dimeric Platinum Phosphinidene Complex

Igor V. Kourkine; David S. Glueck

doi:10.1021/ic970730g

Synthesis and Reactivity of a Dimeric Platinum Phosphinidene Complex

Igor V. Kourkine^*, David S. Glueck

^*Corresponding author for this work

Chemical and Biological Engineering

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Abstract

The dimeric platinum phosphinidene complex [Pt(dppe)(μ-PMes)]₂ (1; dppe = Ph₂PCH₂CH₂PPh₂, Mes = 2,4,6Me₂C₆H₂) was prepared by double deprotonation of [Pt(dppe)(μ-PHMes)]₂[BF₄] (3); use of 1 equiv of base gives the monocationic complex [{Pt(dppe)}₂(μ-PHMes)(μ-PMes)][BF₄] (2), which can also be made from 1 and 1 equiv of HBF₄ NMR data suggest that complex 1 contains pyramidal μ-phosphinidene ligands, and it undergoes nucleophilic reactions typical of a tertiary phosphine. Alkylation with MeI affords [Pt(dppe){μ-P(Me)Mes}]₂[BF₄]₂ (4), BH₃·THF gives the borane adduct [Pt(dppe){μ-P(BH₂)Mes}]₂ (5), and air oxidation yields [Pt(dppe){μ-P(O)Mes}]₂ (6). However, reaction with sulfur gives the monomeric trithioxophosphorane complex Pt(dppe)(S₃PMes) (7), which was prepared independently from Pt(dppe)(trans-stilbene) and [MesPS₂]₂.

Original language	English (US)
Pages (from-to)	5160-5164
Number of pages	5
Journal	Inorganic chemistry
Volume	36
Issue number	23
DOIs	https://doi.org/10.1021/ic970730g
State	Published - 1997

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Physical and Theoretical Chemistry
Inorganic Chemistry

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@article{6028567010394ee7b982b136a75d46da,

title = "Synthesis and Reactivity of a Dimeric Platinum Phosphinidene Complex",

abstract = "The dimeric platinum phosphinidene complex [Pt(dppe)(μ-PMes)]2 (1; dppe = Ph2PCH2CH2PPh2, Mes = 2,4,6Me2C6H2) was prepared by double deprotonation of [Pt(dppe)(μ-PHMes)]2[BF4] (3); use of 1 equiv of base gives the monocationic complex [{Pt(dppe)}2(μ-PHMes)(μ-PMes)][BF4] (2), which can also be made from 1 and 1 equiv of HBF4 NMR data suggest that complex 1 contains pyramidal μ-phosphinidene ligands, and it undergoes nucleophilic reactions typical of a tertiary phosphine. Alkylation with MeI affords [Pt(dppe){μ-P(Me)Mes}]2[BF4]2 (4), BH3·THF gives the borane adduct [Pt(dppe){μ-P(BH2)Mes}]2 (5), and air oxidation yields [Pt(dppe){μ-P(O)Mes}]2 (6). However, reaction with sulfur gives the monomeric trithioxophosphorane complex Pt(dppe)(S3PMes) (7), which was prepared independently from Pt(dppe)(trans-stilbene) and [MesPS2]2.",

author = "Kourkine, {Igor V.} and Glueck, {David S.}",

year = "1997",

doi = "10.1021/ic970730g",

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N2 - The dimeric platinum phosphinidene complex [Pt(dppe)(μ-PMes)]2 (1; dppe = Ph2PCH2CH2PPh2, Mes = 2,4,6Me2C6H2) was prepared by double deprotonation of [Pt(dppe)(μ-PHMes)]2[BF4] (3); use of 1 equiv of base gives the monocationic complex [{Pt(dppe)}2(μ-PHMes)(μ-PMes)][BF4] (2), which can also be made from 1 and 1 equiv of HBF4 NMR data suggest that complex 1 contains pyramidal μ-phosphinidene ligands, and it undergoes nucleophilic reactions typical of a tertiary phosphine. Alkylation with MeI affords [Pt(dppe){μ-P(Me)Mes}]2[BF4]2 (4), BH3·THF gives the borane adduct [Pt(dppe){μ-P(BH2)Mes}]2 (5), and air oxidation yields [Pt(dppe){μ-P(O)Mes}]2 (6). However, reaction with sulfur gives the monomeric trithioxophosphorane complex Pt(dppe)(S3PMes) (7), which was prepared independently from Pt(dppe)(trans-stilbene) and [MesPS2]2.

AB - The dimeric platinum phosphinidene complex [Pt(dppe)(μ-PMes)]2 (1; dppe = Ph2PCH2CH2PPh2, Mes = 2,4,6Me2C6H2) was prepared by double deprotonation of [Pt(dppe)(μ-PHMes)]2[BF4] (3); use of 1 equiv of base gives the monocationic complex [{Pt(dppe)}2(μ-PHMes)(μ-PMes)][BF4] (2), which can also be made from 1 and 1 equiv of HBF4 NMR data suggest that complex 1 contains pyramidal μ-phosphinidene ligands, and it undergoes nucleophilic reactions typical of a tertiary phosphine. Alkylation with MeI affords [Pt(dppe){μ-P(Me)Mes}]2[BF4]2 (4), BH3·THF gives the borane adduct [Pt(dppe){μ-P(BH2)Mes}]2 (5), and air oxidation yields [Pt(dppe){μ-P(O)Mes}]2 (6). However, reaction with sulfur gives the monomeric trithioxophosphorane complex Pt(dppe)(S3PMes) (7), which was prepared independently from Pt(dppe)(trans-stilbene) and [MesPS2]2.

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Synthesis and Reactivity of a Dimeric Platinum Phosphinidene Complex

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