Unexpected Formation of Early Late Heterobimetallic Complexes from Transition Metal Frustrated Lewis Pairs

Andy M. Chapman; Stephanie R Flynn; Duncan F. Wass

doi:10.1021/acs.inorgchem.5b01424

Unexpected Formation of Early Late Heterobimetallic Complexes from Transition Metal Frustrated Lewis Pairs

Andy M. Chapman
, Stephanie R Flynn
, Duncan F. Wass^*

^*Corresponding author for this work

Research output: Contribution to journal › Article (Academic Journal) › peer-review

36 Citations (Scopus)

Abstract

Reaction of transition metal "frustrated" Lewis pair compounds of the type [Cp₂Zr(Me)(OC(CF₃)₂CH₂P^tBu₂)] with the low valent platinum species [Pt(norbornene)₃] leads to the unexpected formation of a heterobimetallic species [Cp₂Zr{Pt(Me)}(OC(CF₃)₂CH₂P^tBu₂)]. Single crystal X-ray analysis reveals an unusual T-shaped geometry at the platinum center, with a relevant C-Pt-P angle of 163.3(3)°. Treatment of this compound with PMe₃ yields [Pt(PMe₃)₄] and regenerates the zirconium precursor. Treatment with [(Et₂O)₂H][B(C₆F₅)₄] protonates off the methyl ligand to give an ether adduct at platinum. Analogous observations are made with titanium-platinum species. We propose the chemistry is best rationalized as a formal insertion of Pt(0) into a Zr-C or Ti-Cl bond.

Original language	English
Pages (from-to)	1017-1021
Number of pages	5
Journal	Inorganic Chemistry
Volume	55
Issue number	3
Early online date	12 Jan 2016
DOIs	https://doi.org/10.1021/acs.inorgchem.5b01424
Publication status	Published - 1 Feb 2016

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title = "Unexpected Formation of Early Late Heterobimetallic Complexes from Transition Metal Frustrated Lewis Pairs",

abstract = "Reaction of transition metal {"}frustrated{"} Lewis pair compounds of the type [Cp2Zr(Me)(OC(CF3)2CH2PtBu2)] with the low valent platinum species [Pt(norbornene)3] leads to the unexpected formation of a heterobimetallic species [Cp2Zr\{Pt(Me)\}(OC(CF3)2CH2PtBu2)]. Single crystal X-ray analysis reveals an unusual T-shaped geometry at the platinum center, with a relevant C-Pt-P angle of 163.3(3)°. Treatment of this compound with PMe3 yields [Pt(PMe3)4] and regenerates the zirconium precursor. Treatment with [(Et2O)2H][B(C6F5)4] protonates off the methyl ligand to give an ether adduct at platinum. Analogous observations are made with titanium-platinum species. We propose the chemistry is best rationalized as a formal insertion of Pt(0) into a Zr-C or Ti-Cl bond.",

author = "Chapman, \{Andy M.\} and Flynn, \{Stephanie R\} and Wass, \{Duncan F.\}",

year = "2016",

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doi = "10.1021/acs.inorgchem.5b01424",

language = "English",

volume = "55",

pages = "1017--1021",

journal = "Inorganic Chemistry",

issn = "0020-1669",

publisher = "American Chemical Society",

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TY - JOUR

T1 - Unexpected Formation of Early Late Heterobimetallic Complexes from Transition Metal Frustrated Lewis Pairs

AU - Chapman, Andy M.

AU - Flynn, Stephanie R

AU - Wass, Duncan F.

PY - 2016/2/1

Y1 - 2016/2/1

N2 - Reaction of transition metal "frustrated" Lewis pair compounds of the type [Cp2Zr(Me)(OC(CF3)2CH2PtBu2)] with the low valent platinum species [Pt(norbornene)3] leads to the unexpected formation of a heterobimetallic species [Cp2Zr{Pt(Me)}(OC(CF3)2CH2PtBu2)]. Single crystal X-ray analysis reveals an unusual T-shaped geometry at the platinum center, with a relevant C-Pt-P angle of 163.3(3)°. Treatment of this compound with PMe3 yields [Pt(PMe3)4] and regenerates the zirconium precursor. Treatment with [(Et2O)2H][B(C6F5)4] protonates off the methyl ligand to give an ether adduct at platinum. Analogous observations are made with titanium-platinum species. We propose the chemistry is best rationalized as a formal insertion of Pt(0) into a Zr-C or Ti-Cl bond.

AB - Reaction of transition metal "frustrated" Lewis pair compounds of the type [Cp2Zr(Me)(OC(CF3)2CH2PtBu2)] with the low valent platinum species [Pt(norbornene)3] leads to the unexpected formation of a heterobimetallic species [Cp2Zr{Pt(Me)}(OC(CF3)2CH2PtBu2)]. Single crystal X-ray analysis reveals an unusual T-shaped geometry at the platinum center, with a relevant C-Pt-P angle of 163.3(3)°. Treatment of this compound with PMe3 yields [Pt(PMe3)4] and regenerates the zirconium precursor. Treatment with [(Et2O)2H][B(C6F5)4] protonates off the methyl ligand to give an ether adduct at platinum. Analogous observations are made with titanium-platinum species. We propose the chemistry is best rationalized as a formal insertion of Pt(0) into a Zr-C or Ti-Cl bond.

UR - https://www.scopus.com/pages/publications/84956607758

U2 - 10.1021/acs.inorgchem.5b01424

DO - 10.1021/acs.inorgchem.5b01424

M3 - Article (Academic Journal)

C2 - 26756975

AN - SCOPUS:84956607758

SN - 0020-1669

VL - 55

SP - 1017

EP - 1021

JO - Inorganic Chemistry

JF - Inorganic Chemistry

IS - 3

ER -

Unexpected Formation of Early Late Heterobimetallic Complexes from Transition Metal Frustrated Lewis Pairs

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