Phosphaisonitrile umpolung-synthesis and reactivity of chloro aminophosphino carbynes

Annie L. Colebatch; Benjamin J. Frogley; Anthony F. Hill

doi:10.1039/c9dt01838g

Phosphaisonitrile umpolung-synthesis and reactivity of chloro aminophosphino carbynes

Annie L. Colebatch, Benjamin J. Frogley, Anthony F. Hill^*

^*Corresponding author for this work

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

9 Citations (Scopus)

Abstract

Sequential treatment of [W(CBr)(CO)₂(Tp∗)] (Tp∗ = hydrotris(dimethylpyrazolyl)borate) with ⁿBuLi and Cl₂PNⁱPr₂ provides the aminochlorophosphinocarbyne [W(CPClNⁱPr₂)(CO)₂(Tp∗)]. The chloro substituent undergoes subsitution with RLi (R = Me, Et, Ph) to afford [W(CPRNⁱPr₂)(CO)₂(Tp∗)] and with [W(CLi)(CO)₂(Tp∗)] to give the aminobis(alkylidynyl)phosphine [ⁱPr₂NP{CW(CO)₂(Tp∗)}₂]. Treatment with Li[BHEt₃] gives the primary aminophosphine [W(CPHNⁱPr₂)(CO)₂(Tp∗)], formed in a mixture with the ethyl derivative [W(CPEtNⁱPr₂)(CO)₂(Tp∗)]. Although they could not be isolated, spectroscopic data indicated that halide abstraction with Al₂Cl₆ forms the phosphaisonitrile salt [W(CPNⁱPr₂)(CO)₂(Tp∗)][AlCl₄], which displays electrophilic character at phosphorus, e.g., in the reaction with diphenylacetylene to furnish the phosphirenium salt [W{CP(C₂Ph₂)NⁱPr₂}(CO)₂(Tp∗)][AlCl₄]. Finally, the reaction with LiNPh₂ gives the mixed diaminophosphinocarbyne, [W{CP(NⁱPr₂)(NPh₂)}(CO)₂(Tp∗)].

Original language	English
Pages (from-to)	10628-10641
Number of pages	14
Journal	Dalton Transactions
Volume	48
Issue number	28
DOIs	https://doi.org/10.1039/c9dt01838g
Publication status	Published - 2019

Access to Document

10.1039/c9dt01838g

Cite this

@article{0552a4b674514285b6195737e6446da0,

title = "Phosphaisonitrile umpolung-synthesis and reactivity of chloro aminophosphino carbynes",

abstract = "Sequential treatment of [W(CBr)(CO)2(Tp∗)] (Tp∗ = hydrotris(dimethylpyrazolyl)borate) with nBuLi and Cl2PNiPr2 provides the aminochlorophosphinocarbyne [W(CPClNiPr2)(CO)2(Tp∗)]. The chloro substituent undergoes subsitution with RLi (R = Me, Et, Ph) to afford [W(CPRNiPr2)(CO)2(Tp∗)] and with [W(CLi)(CO)2(Tp∗)] to give the aminobis(alkylidynyl)phosphine [iPr2NP{CW(CO)2(Tp∗)}2]. Treatment with Li[BHEt3] gives the primary aminophosphine [W(CPHNiPr2)(CO)2(Tp∗)], formed in a mixture with the ethyl derivative [W(CPEtNiPr2)(CO)2(Tp∗)]. Although they could not be isolated, spectroscopic data indicated that halide abstraction with Al2Cl6 forms the phosphaisonitrile salt [W(CPNiPr2)(CO)2(Tp∗)][AlCl4], which displays electrophilic character at phosphorus, e.g., in the reaction with diphenylacetylene to furnish the phosphirenium salt [W{CP(C2Ph2)NiPr2}(CO)2(Tp∗)][AlCl4]. Finally, the reaction with LiNPh2 gives the mixed diaminophosphinocarbyne, [W{CP(NiPr2)(NPh2)}(CO)2(Tp∗)].",

author = "Colebatch, {Annie L.} and Frogley, {Benjamin J.} and Hill, {Anthony F.}",

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

year = "2019",

doi = "10.1039/c9dt01838g",

language = "English",

volume = "48",

pages = "10628--10641",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "28",

}

TY - JOUR

T1 - Phosphaisonitrile umpolung-synthesis and reactivity of chloro aminophosphino carbynes

AU - Colebatch, Annie L.

AU - Frogley, Benjamin J.

AU - Hill, Anthony F.

PY - 2019

Y1 - 2019

N2 - Sequential treatment of [W(CBr)(CO)2(Tp∗)] (Tp∗ = hydrotris(dimethylpyrazolyl)borate) with nBuLi and Cl2PNiPr2 provides the aminochlorophosphinocarbyne [W(CPClNiPr2)(CO)2(Tp∗)]. The chloro substituent undergoes subsitution with RLi (R = Me, Et, Ph) to afford [W(CPRNiPr2)(CO)2(Tp∗)] and with [W(CLi)(CO)2(Tp∗)] to give the aminobis(alkylidynyl)phosphine [iPr2NP{CW(CO)2(Tp∗)}2]. Treatment with Li[BHEt3] gives the primary aminophosphine [W(CPHNiPr2)(CO)2(Tp∗)], formed in a mixture with the ethyl derivative [W(CPEtNiPr2)(CO)2(Tp∗)]. Although they could not be isolated, spectroscopic data indicated that halide abstraction with Al2Cl6 forms the phosphaisonitrile salt [W(CPNiPr2)(CO)2(Tp∗)][AlCl4], which displays electrophilic character at phosphorus, e.g., in the reaction with diphenylacetylene to furnish the phosphirenium salt [W{CP(C2Ph2)NiPr2}(CO)2(Tp∗)][AlCl4]. Finally, the reaction with LiNPh2 gives the mixed diaminophosphinocarbyne, [W{CP(NiPr2)(NPh2)}(CO)2(Tp∗)].

AB - Sequential treatment of [W(CBr)(CO)2(Tp∗)] (Tp∗ = hydrotris(dimethylpyrazolyl)borate) with nBuLi and Cl2PNiPr2 provides the aminochlorophosphinocarbyne [W(CPClNiPr2)(CO)2(Tp∗)]. The chloro substituent undergoes subsitution with RLi (R = Me, Et, Ph) to afford [W(CPRNiPr2)(CO)2(Tp∗)] and with [W(CLi)(CO)2(Tp∗)] to give the aminobis(alkylidynyl)phosphine [iPr2NP{CW(CO)2(Tp∗)}2]. Treatment with Li[BHEt3] gives the primary aminophosphine [W(CPHNiPr2)(CO)2(Tp∗)], formed in a mixture with the ethyl derivative [W(CPEtNiPr2)(CO)2(Tp∗)]. Although they could not be isolated, spectroscopic data indicated that halide abstraction with Al2Cl6 forms the phosphaisonitrile salt [W(CPNiPr2)(CO)2(Tp∗)][AlCl4], which displays electrophilic character at phosphorus, e.g., in the reaction with diphenylacetylene to furnish the phosphirenium salt [W{CP(C2Ph2)NiPr2}(CO)2(Tp∗)][AlCl4]. Finally, the reaction with LiNPh2 gives the mixed diaminophosphinocarbyne, [W{CP(NiPr2)(NPh2)}(CO)2(Tp∗)].

UR - http://www.scopus.com/inward/record.url?scp=85069044218&partnerID=8YFLogxK

U2 - 10.1039/c9dt01838g

DO - 10.1039/c9dt01838g

M3 - Article

SN - 1477-9226

VL - 48

SP - 10628

EP - 10641

JO - Dalton Transactions

JF - Dalton Transactions

IS - 28

ER -

Phosphaisonitrile umpolung-synthesis and reactivity of chloro aminophosphino carbynes

Abstract

Access to Document

Other files and links

Fingerprint

Cite this