The interplay of bis(tricarbido) and dimetallaoctatetrayne complexes of platinum

Rian D. Dewhurst; Anthony F. Hill; Anthony C. Willis

doi:10.1021/om900485b

The interplay of bis(tricarbido) and dimetallaoctatetrayne complexes of platinum

Rian D. Dewhurst, Anthony F. Hill, Anthony C. Willis

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12 Citations (Scopus)

Abstract

Non-interconvertible platinum bis(tricarbidotungsten) and dimetallaoctatetrayne π-complexes arise from the reactions of bis(tricarbidotungsten)mercurials and aurates with complexes of platinum(0) and platmum(II). Thus [PtCl₂(PPh₃)₂] with either [Hg{C₃W(CO)₂(Tp^*)}₂] or PPN[Au-{C₃W(CO)₂(Tp^*))}] (Tp ^*) = hydrotris(3,5-dimethylpyrazol-1-y1)borate) affords both cis-[Pt{C₃W-(CO)₂(Tp^*)}, (PPh ₃)₂] and [(Tp^*)(CO)₂WC ₆W(CO)₂(Tp^*)], while the latter with [Pt(C₂H₄)(PPh₃)₂] affords the π-complex [Pt{η²∼(Tp^*)(CO) ₂WC₆W(c6)₂(Tp^*)}(PPh ₃)₂], which does not convert to the bis(tricarbido) isomer. Although an intermediate bis(tricarbidotungsten) complex [Pt{C ₃W(CO)₂-(Tp^*)}₂(dppe)] (dppe = 1,2-bis(diphenylphosphine)ethane) may be spectroscopically observed to form in the related reaction employing [PtCl₂(dppe)], this is unstable, ultimately and exclusively evolving to the free dimetallaoctatetrayne. The reaction of [Pt(C₂H₄)(PPh₃)₂] with [Hg{C₃W(CO)₂-(Tp^*)}₂] provides a ca 3:2 mixture of m-[Pt{C₃W(CO)₂(Tp^*)} ₂(PPh₃)₂] and [Pt{η²-(Tp ^*)(CO)₂WC₆-W(CO)₂(Tp ^*)}(PPh₃)₂] in addition to traces of [(Tp^*)(CO)₂WC₆W(CO)₂(Tp ^*)]. Circumstantial evidence is presented to suggest that the mercuric chloride liberated in the transmetalation reaction plays a role in subsequent transformations.

Original language	English
Pages (from-to)	4735-4740
Number of pages	6
Journal	Organometallics
Volume	28
Issue number	16
DOIs	https://doi.org/10.1021/om900485b
Publication status	Published - 24 Aug 2009

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@article{5e44079032ca4ade84eb16f49e0292a2,

title = "The interplay of bis(tricarbido) and dimetallaoctatetrayne complexes of platinum",

abstract = "Non-interconvertible platinum bis(tricarbidotungsten) and dimetallaoctatetrayne π-complexes arise from the reactions of bis(tricarbidotungsten)mercurials and aurates with complexes of platinum(0) and platmum(II). Thus [PtCl2(PPh3)2] with either [Hg\{C3W(CO)2(Tp*)\}2] or PPN[Au-\{C3W(CO)2(Tp*))\}] (Tp *) = hydrotris(3,5-dimethylpyrazol-1-y1)borate) affords both cis-[Pt\{C3W-(CO)2(Tp*)\}, (PPh 3)2] and [(Tp*)(CO)2WC 6W(CO)2(Tp*)], while the latter with [Pt(C2H4)(PPh3)2] affords the π-complex [Pt\{η2∼(Tp*)(CO) 2WC6W(c6)2(Tp*)\}(PPh 3)2], which does not convert to the bis(tricarbido) isomer. Although an intermediate bis(tricarbidotungsten) complex [Pt\{C 3W(CO)2-(Tp*)\}2(dppe)] (dppe = 1,2-bis(diphenylphosphine)ethane) may be spectroscopically observed to form in the related reaction employing [PtCl2(dppe)], this is unstable, ultimately and exclusively evolving to the free dimetallaoctatetrayne. The reaction of [Pt(C2H4)(PPh3)2] with [Hg\{C3W(CO)2-(Tp*)\}2] provides a ca 3:2 mixture of m-[Pt\{C3W(CO)2(Tp*)\} 2(PPh3)2] and [Pt\{η2-(Tp *)(CO)2WC6-W(CO)2(Tp *)\}(PPh3)2] in addition to traces of [(Tp*)(CO)2WC6W(CO)2(Tp *)]. Circumstantial evidence is presented to suggest that the mercuric chloride liberated in the transmetalation reaction plays a role in subsequent transformations.",

author = "Dewhurst, \{Rian D.\} and Hill, \{Anthony F.\} and Willis, \{Anthony C.\}",

year = "2009",

month = aug,

day = "24",

doi = "10.1021/om900485b",

language = "English",

volume = "28",

pages = "4735--4740",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "16",

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TY - JOUR

T1 - The interplay of bis(tricarbido) and dimetallaoctatetrayne complexes of platinum

AU - Dewhurst, Rian D.

AU - Hill, Anthony F.

AU - Willis, Anthony C.

PY - 2009/8/24

Y1 - 2009/8/24

N2 - Non-interconvertible platinum bis(tricarbidotungsten) and dimetallaoctatetrayne π-complexes arise from the reactions of bis(tricarbidotungsten)mercurials and aurates with complexes of platinum(0) and platmum(II). Thus [PtCl2(PPh3)2] with either [Hg{C3W(CO)2(Tp*)}2] or PPN[Au-{C3W(CO)2(Tp*))}] (Tp *) = hydrotris(3,5-dimethylpyrazol-1-y1)borate) affords both cis-[Pt{C3W-(CO)2(Tp*)}, (PPh 3)2] and [(Tp*)(CO)2WC 6W(CO)2(Tp*)], while the latter with [Pt(C2H4)(PPh3)2] affords the π-complex [Pt{η2∼(Tp*)(CO) 2WC6W(c6)2(Tp*)}(PPh 3)2], which does not convert to the bis(tricarbido) isomer. Although an intermediate bis(tricarbidotungsten) complex [Pt{C 3W(CO)2-(Tp*)}2(dppe)] (dppe = 1,2-bis(diphenylphosphine)ethane) may be spectroscopically observed to form in the related reaction employing [PtCl2(dppe)], this is unstable, ultimately and exclusively evolving to the free dimetallaoctatetrayne. The reaction of [Pt(C2H4)(PPh3)2] with [Hg{C3W(CO)2-(Tp*)}2] provides a ca 3:2 mixture of m-[Pt{C3W(CO)2(Tp*)} 2(PPh3)2] and [Pt{η2-(Tp *)(CO)2WC6-W(CO)2(Tp *)}(PPh3)2] in addition to traces of [(Tp*)(CO)2WC6W(CO)2(Tp *)]. Circumstantial evidence is presented to suggest that the mercuric chloride liberated in the transmetalation reaction plays a role in subsequent transformations.

AB - Non-interconvertible platinum bis(tricarbidotungsten) and dimetallaoctatetrayne π-complexes arise from the reactions of bis(tricarbidotungsten)mercurials and aurates with complexes of platinum(0) and platmum(II). Thus [PtCl2(PPh3)2] with either [Hg{C3W(CO)2(Tp*)}2] or PPN[Au-{C3W(CO)2(Tp*))}] (Tp *) = hydrotris(3,5-dimethylpyrazol-1-y1)borate) affords both cis-[Pt{C3W-(CO)2(Tp*)}, (PPh 3)2] and [(Tp*)(CO)2WC 6W(CO)2(Tp*)], while the latter with [Pt(C2H4)(PPh3)2] affords the π-complex [Pt{η2∼(Tp*)(CO) 2WC6W(c6)2(Tp*)}(PPh 3)2], which does not convert to the bis(tricarbido) isomer. Although an intermediate bis(tricarbidotungsten) complex [Pt{C 3W(CO)2-(Tp*)}2(dppe)] (dppe = 1,2-bis(diphenylphosphine)ethane) may be spectroscopically observed to form in the related reaction employing [PtCl2(dppe)], this is unstable, ultimately and exclusively evolving to the free dimetallaoctatetrayne. The reaction of [Pt(C2H4)(PPh3)2] with [Hg{C3W(CO)2-(Tp*)}2] provides a ca 3:2 mixture of m-[Pt{C3W(CO)2(Tp*)} 2(PPh3)2] and [Pt{η2-(Tp *)(CO)2WC6-W(CO)2(Tp *)}(PPh3)2] in addition to traces of [(Tp*)(CO)2WC6W(CO)2(Tp *)]. Circumstantial evidence is presented to suggest that the mercuric chloride liberated in the transmetalation reaction plays a role in subsequent transformations.

UR - https://www.scopus.com/pages/publications/68949194747

U2 - 10.1021/om900485b

DO - 10.1021/om900485b

M3 - Article

SN - 0276-7333

VL - 28

SP - 4735

EP - 4740

JO - Organometallics

JF - Organometallics

IS - 16

ER -

The interplay of bis(tricarbido) and dimetallaoctatetrayne complexes of platinum

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