Alkynylselenolatoalkylidynes (LnMC-Se-CCR) as building blocks for mixed metal/main-group extended frameworks

Benjamin J. Frogley; Tobias L. Genet; Anthony F. Hill; Chee S. Onn

doi:10.1039/c9dt01504c

Alkynylselenolatoalkylidynes (L_nMC-Se-CCR) as building blocks for mixed metal/main-group extended frameworks

Benjamin J. Frogley
, Tobias L. Genet
, Anthony F. Hill^*
, Chee S. Onn

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

8 Citations (Scopus)

Abstract

The reactions of [W(CBr)(CO)₂(Tp∗)] (Tp∗ = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with lithium alkynylselenolates LiSeCCR (R = SiMe₃, SiⁱPr₃, ⁿBu, ^tBu, Ph, p-tolyl) afford the alkynylselenolatoalkylidyne complexes [W(CSeCCR)(CO)₂(Tp∗)]. Desilylation of the SiMe₃ complex furnishes the parent [W(CSeCCH)(CO)₂(Tp∗)], which may be further derivatised by deprotonation and treatment with triphenylcarbenium or triphenylmetal chlorides to give mixed-heteroatom products [W(CSeCCEPh₃)(CO)₂(Tp∗)] (E = C, Si, Ge, Sn, Pb). This procedure extends to dichlorosilanes, whereby the unusual bimetallic complexes [(Tp∗)(CO)₂WCSeCCSiRR′CCSeCW(CO)₂(Tp∗)] (R, R′ = Ph, CH₃) are obtained, bridged by unsaturated units interrupted by two different main-group heteroatoms. Finally, the trimetallic analogues, [{(Tp∗)(CO)₂W(CSeCC)}₃SiR] (R = Ph, Et), may be prepared in the same manner from appropriate organotrichlorosilanes.

Original language	English
Pages (from-to)	7632-7643
Number of pages	12
Journal	Dalton Transactions
Volume	48
Issue number	22
DOIs	https://doi.org/10.1039/c9dt01504c
Publication status	Published - 2019

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@article{6adb4d4ab8d64f8c9edb39f28aeb953c,

title = "Alkynylselenolatoalkylidynes (LnMC-Se-CCR) as building blocks for mixed metal/main-group extended frameworks",

abstract = "The reactions of [W(CBr)(CO)2(Tp∗)] (Tp∗ = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with lithium alkynylselenolates LiSeCCR (R = SiMe3, SiiPr3, nBu, tBu, Ph, p-tolyl) afford the alkynylselenolatoalkylidyne complexes [W(CSeCCR)(CO)2(Tp∗)]. Desilylation of the SiMe3 complex furnishes the parent [W(CSeCCH)(CO)2(Tp∗)], which may be further derivatised by deprotonation and treatment with triphenylcarbenium or triphenylmetal chlorides to give mixed-heteroatom products [W(CSeCCEPh3)(CO)2(Tp∗)] (E = C, Si, Ge, Sn, Pb). This procedure extends to dichlorosilanes, whereby the unusual bimetallic complexes [(Tp∗)(CO)2WCSeCCSiRR′CCSeCW(CO)2(Tp∗)] (R, R′ = Ph, CH3) are obtained, bridged by unsaturated units interrupted by two different main-group heteroatoms. Finally, the trimetallic analogues, [\{(Tp∗)(CO)2W(CSeCC)\}3SiR] (R = Ph, Et), may be prepared in the same manner from appropriate organotrichlorosilanes.",

author = "Frogley, \{Benjamin J.\} and Genet, \{Tobias L.\} and Hill, \{Anthony F.\} and Onn, \{Chee S.\}",

note = "Publisher Copyright: {\textcopyright} The Royal Society of Chemistry 2019.",

year = "2019",

doi = "10.1039/c9dt01504c",

language = "English",

volume = "48",

pages = "7632--7643",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "22",

}

TY - JOUR

T1 - Alkynylselenolatoalkylidynes (LnMC-Se-CCR) as building blocks for mixed metal/main-group extended frameworks

AU - Frogley, Benjamin J.

AU - Genet, Tobias L.

AU - Hill, Anthony F.

AU - Onn, Chee S.

PY - 2019

Y1 - 2019

N2 - The reactions of [W(CBr)(CO)2(Tp∗)] (Tp∗ = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with lithium alkynylselenolates LiSeCCR (R = SiMe3, SiiPr3, nBu, tBu, Ph, p-tolyl) afford the alkynylselenolatoalkylidyne complexes [W(CSeCCR)(CO)2(Tp∗)]. Desilylation of the SiMe3 complex furnishes the parent [W(CSeCCH)(CO)2(Tp∗)], which may be further derivatised by deprotonation and treatment with triphenylcarbenium or triphenylmetal chlorides to give mixed-heteroatom products [W(CSeCCEPh3)(CO)2(Tp∗)] (E = C, Si, Ge, Sn, Pb). This procedure extends to dichlorosilanes, whereby the unusual bimetallic complexes [(Tp∗)(CO)2WCSeCCSiRR′CCSeCW(CO)2(Tp∗)] (R, R′ = Ph, CH3) are obtained, bridged by unsaturated units interrupted by two different main-group heteroatoms. Finally, the trimetallic analogues, [{(Tp∗)(CO)2W(CSeCC)}3SiR] (R = Ph, Et), may be prepared in the same manner from appropriate organotrichlorosilanes.

AB - The reactions of [W(CBr)(CO)2(Tp∗)] (Tp∗ = hydrotris(3,5-dimethylpyrazol-1-yl)borate) with lithium alkynylselenolates LiSeCCR (R = SiMe3, SiiPr3, nBu, tBu, Ph, p-tolyl) afford the alkynylselenolatoalkylidyne complexes [W(CSeCCR)(CO)2(Tp∗)]. Desilylation of the SiMe3 complex furnishes the parent [W(CSeCCH)(CO)2(Tp∗)], which may be further derivatised by deprotonation and treatment with triphenylcarbenium or triphenylmetal chlorides to give mixed-heteroatom products [W(CSeCCEPh3)(CO)2(Tp∗)] (E = C, Si, Ge, Sn, Pb). This procedure extends to dichlorosilanes, whereby the unusual bimetallic complexes [(Tp∗)(CO)2WCSeCCSiRR′CCSeCW(CO)2(Tp∗)] (R, R′ = Ph, CH3) are obtained, bridged by unsaturated units interrupted by two different main-group heteroatoms. Finally, the trimetallic analogues, [{(Tp∗)(CO)2W(CSeCC)}3SiR] (R = Ph, Et), may be prepared in the same manner from appropriate organotrichlorosilanes.

UR - https://www.scopus.com/pages/publications/85066848701

U2 - 10.1039/c9dt01504c

DO - 10.1039/c9dt01504c

M3 - Article

SN - 1477-9226

VL - 48

SP - 7632

EP - 7643

JO - Dalton Transactions

JF - Dalton Transactions

IS - 22

ER -

Alkynylselenolatoalkylidynes (L_nMC-Se-CCR) as building blocks for mixed metal/main-group extended frameworks

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