Highly Selective Substitution and Insertion Reactions of Silylenes in a Metal-Coordinated Polyphosphide

Ravi Yadav; Thomas Simler; Stephan Reichl; Bhupendra Goswami; Christoph Schoo; Ralf Köppe; Manfred Scheer; Peter W. Roesky

doi:10.1021/jacs.9b12151

Highly Selective Substitution and Insertion Reactions of Silylenes in a Metal-Coordinated Polyphosphide

Ravi Yadav
, Thomas Simler
, Stephan Reichl
, Bhupendra Goswami
, Christoph Schoo
, Ralf Köppe
, Manfred Scheer
, Peter W. Roesky

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

Abstract

Selective substitution and insertion reactions of silylenes into the cyclo-P₅ ring of [Cp∗Fe(ν⁵-P₅)] are reported. The selective substitution of one P atom by an isoelectronic [LSi] fragment (L = PhC(N^tBu)₂) leads to [(ν⁴-P₄SiL)FeCp∗] and [LSi(Cl)=P-SiL(Cl)₂]. To elucidate the reaction mechanism, [{LSi(N(SiMe₃)₂)}{(ν⁴-P₅)FeCp∗}], in which the silicon atom binds to the cyclo-P₅ ring, was synthesized as a model compound for the reaction intermediate. The insertion of [LSi-SiL] into the cyclo-P₅ ring of [Cp∗Fe(ν⁵-P₅)] resulted in [{ν⁴-P₅(SiL)₂}FeCp∗] featuring a cyclo-P₅(SiL)₂ ring, which corresponds to the largest silicon-polyphosphorus ring known in a complex.

Original language	English
Pages (from-to)	1190-1195
Number of pages	6
Journal	Journal of the American Chemical Society
Volume	142
Issue number	3
DOIs	https://doi.org/10.1021/jacs.9b12151
Publication status	Published - 22 Jan 2020
Externally published	Yes

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@article{893ce8ee655749faa7ec4a4d9ef479bf,

title = "Highly Selective Substitution and Insertion Reactions of Silylenes in a Metal-Coordinated Polyphosphide",

abstract = "Selective substitution and insertion reactions of silylenes into the cyclo-P5 ring of [Cp∗Fe(ν5-P5)] are reported. The selective substitution of one P atom by an isoelectronic [LSi] fragment (L = PhC(NtBu)2) leads to [(ν4-P4SiL)FeCp∗] and [LSi(Cl)=P-SiL(Cl)2]. To elucidate the reaction mechanism, [\{LSi(N(SiMe3)2)\}\{(ν4-P5)FeCp∗\}], in which the silicon atom binds to the cyclo-P5 ring, was synthesized as a model compound for the reaction intermediate. The insertion of [LSi-SiL] into the cyclo-P5 ring of [Cp∗Fe(ν5-P5)] resulted in [\{ν4-P5(SiL)2\}FeCp∗] featuring a cyclo-P5(SiL)2 ring, which corresponds to the largest silicon-polyphosphorus ring known in a complex.",

author = "Ravi Yadav and Thomas Simler and Stephan Reichl and Bhupendra Goswami and Christoph Schoo and Ralf K{\"o}ppe and Manfred Scheer and Roesky, \{Peter W.\}",

note = "Publisher Copyright: {\textcopyright} 2019 American Chemical Society.",

year = "2020",

month = jan,

day = "22",

doi = "10.1021/jacs.9b12151",

language = "English",

volume = "142",

pages = "1190--1195",

journal = "Journal of the American Chemical Society",

issn = "0002-7863",

number = "3",

}

TY - JOUR

T1 - Highly Selective Substitution and Insertion Reactions of Silylenes in a Metal-Coordinated Polyphosphide

AU - Yadav, Ravi

AU - Simler, Thomas

AU - Reichl, Stephan

AU - Goswami, Bhupendra

AU - Schoo, Christoph

AU - Köppe, Ralf

AU - Scheer, Manfred

AU - Roesky, Peter W.

PY - 2020/1/22

Y1 - 2020/1/22

N2 - Selective substitution and insertion reactions of silylenes into the cyclo-P5 ring of [Cp∗Fe(ν5-P5)] are reported. The selective substitution of one P atom by an isoelectronic [LSi] fragment (L = PhC(NtBu)2) leads to [(ν4-P4SiL)FeCp∗] and [LSi(Cl)=P-SiL(Cl)2]. To elucidate the reaction mechanism, [{LSi(N(SiMe3)2)}{(ν4-P5)FeCp∗}], in which the silicon atom binds to the cyclo-P5 ring, was synthesized as a model compound for the reaction intermediate. The insertion of [LSi-SiL] into the cyclo-P5 ring of [Cp∗Fe(ν5-P5)] resulted in [{ν4-P5(SiL)2}FeCp∗] featuring a cyclo-P5(SiL)2 ring, which corresponds to the largest silicon-polyphosphorus ring known in a complex.

AB - Selective substitution and insertion reactions of silylenes into the cyclo-P5 ring of [Cp∗Fe(ν5-P5)] are reported. The selective substitution of one P atom by an isoelectronic [LSi] fragment (L = PhC(NtBu)2) leads to [(ν4-P4SiL)FeCp∗] and [LSi(Cl)=P-SiL(Cl)2]. To elucidate the reaction mechanism, [{LSi(N(SiMe3)2)}{(ν4-P5)FeCp∗}], in which the silicon atom binds to the cyclo-P5 ring, was synthesized as a model compound for the reaction intermediate. The insertion of [LSi-SiL] into the cyclo-P5 ring of [Cp∗Fe(ν5-P5)] resulted in [{ν4-P5(SiL)2}FeCp∗] featuring a cyclo-P5(SiL)2 ring, which corresponds to the largest silicon-polyphosphorus ring known in a complex.

U2 - 10.1021/jacs.9b12151

DO - 10.1021/jacs.9b12151

M3 - Article

C2 - 31860286

AN - SCOPUS:85078334352

SN - 0002-7863

VL - 142

SP - 1190

EP - 1195

JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

IS - 3

ER -

Highly Selective Substitution and Insertion Reactions of Silylenes in a Metal-Coordinated Polyphosphide

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