Distinct modes of Si-H binding to Rh in complexes of a phosphine-diarylamido-silane (SiNP) pincer ligand

A. Rain Talosig; Mario N. Cosio; Benjamin Morse; Vinh T. Nguyen; Alex J. Kosanovich; Christopher J. Pell; Chun Li; Nattamai Bhuvanesh; Jia Zhou; Anna S. Larsen; Oleg V. Ozerov

doi:10.1039/d2dt02175g

Distinct modes of Si-H binding to Rh in complexes of a phosphine-diarylamido-silane (SiNP) pincer ligand

A. Rain Talosig
, Mario N. Cosio
, Benjamin Morse
, Vinh T. Nguyen
, Alex J. Kosanovich
, Christopher J. Pell
, Chun Li
, Nattamai Bhuvanesh
, Jia Zhou^*
, Anna S. Larsen^*
, Oleg V. Ozerov^*

^*Corresponding author for this work

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

1 Scopus citations

Abstract

Syntheses of Rh complexes of the phosphine-amido-silane SiNP ligand are reported. The reaction of the parent (SiNP)H ligand (4) with 0.5 equiv. [(COE)RhCl]₂ (COE = cis-cyclooctene) in the presence of NaN(SiME₃)₂ resulted in the formation of (SiNP)Rh(COE) (5). Compound 5 was converted to a series of (SiNP)Rh(P(OR)₃) complexes 6-10 (R = Ph, ⁱPr, ⁿBu, Et, or Me) by treatment with the corresponding phosphite. NMR and XRD structural data, as well as the DFT computational analysis indicate that compounds 5-10 are divided into two structural Types (A and B), differing in the nature of the interaction of the Si-H bond of the SiNP ligand with Rh.

Original language	English
Pages (from-to)	14150-14155
Number of pages	6
Journal	Dalton Transactions
Volume	51
Issue number	37
DOIs	https://doi.org/10.1039/d2dt02175g
State	Published - 25 Aug 2022
Externally published	Yes

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title = "Distinct modes of Si-H binding to Rh in complexes of a phosphine-diarylamido-silane (SiNP) pincer ligand",

abstract = "Syntheses of Rh complexes of the phosphine-amido-silane SiNP ligand are reported. The reaction of the parent (SiNP)H ligand (4) with 0.5 equiv. [(COE)RhCl]2 (COE = cis-cyclooctene) in the presence of NaN(SiME3)2 resulted in the formation of (SiNP)Rh(COE) (5). Compound 5 was converted to a series of (SiNP)Rh(P(OR)3) complexes 6-10 (R = Ph, iPr, nBu, Et, or Me) by treatment with the corresponding phosphite. NMR and XRD structural data, as well as the DFT computational analysis indicate that compounds 5-10 are divided into two structural Types (A and B), differing in the nature of the interaction of the Si-H bond of the SiNP ligand with Rh.",

author = "\{Rain Talosig\}, A. and Cosio, \{Mario N.\} and Benjamin Morse and Nguyen, \{Vinh T.\} and Kosanovich, \{Alex J.\} and Pell, \{Christopher J.\} and Chun Li and Nattamai Bhuvanesh and Jia Zhou and Larsen, \{Anna S.\} and Ozerov, \{Oleg V.\}",

note = "Publisher Copyright: {\textcopyright} 2022 The Royal Society of Chemistry.",

year = "2022",

month = aug,

day = "25",

doi = "10.1039/d2dt02175g",

language = "英语",

volume = "51",

pages = "14150--14155",

journal = "Dalton Transactions",

issn = "1477-9226",

publisher = "Royal Society of Chemistry",

number = "37",

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TY - JOUR

T1 - Distinct modes of Si-H binding to Rh in complexes of a phosphine-diarylamido-silane (SiNP) pincer ligand

AU - Rain Talosig, A.

AU - Cosio, Mario N.

AU - Morse, Benjamin

AU - Nguyen, Vinh T.

AU - Kosanovich, Alex J.

AU - Pell, Christopher J.

AU - Li, Chun

AU - Bhuvanesh, Nattamai

AU - Zhou, Jia

AU - Larsen, Anna S.

AU - Ozerov, Oleg V.

PY - 2022/8/25

Y1 - 2022/8/25

N2 - Syntheses of Rh complexes of the phosphine-amido-silane SiNP ligand are reported. The reaction of the parent (SiNP)H ligand (4) with 0.5 equiv. [(COE)RhCl]2 (COE = cis-cyclooctene) in the presence of NaN(SiME3)2 resulted in the formation of (SiNP)Rh(COE) (5). Compound 5 was converted to a series of (SiNP)Rh(P(OR)3) complexes 6-10 (R = Ph, iPr, nBu, Et, or Me) by treatment with the corresponding phosphite. NMR and XRD structural data, as well as the DFT computational analysis indicate that compounds 5-10 are divided into two structural Types (A and B), differing in the nature of the interaction of the Si-H bond of the SiNP ligand with Rh.

AB - Syntheses of Rh complexes of the phosphine-amido-silane SiNP ligand are reported. The reaction of the parent (SiNP)H ligand (4) with 0.5 equiv. [(COE)RhCl]2 (COE = cis-cyclooctene) in the presence of NaN(SiME3)2 resulted in the formation of (SiNP)Rh(COE) (5). Compound 5 was converted to a series of (SiNP)Rh(P(OR)3) complexes 6-10 (R = Ph, iPr, nBu, Et, or Me) by treatment with the corresponding phosphite. NMR and XRD structural data, as well as the DFT computational analysis indicate that compounds 5-10 are divided into two structural Types (A and B), differing in the nature of the interaction of the Si-H bond of the SiNP ligand with Rh.

UR - https://www.scopus.com/pages/publications/85138634297

U2 - 10.1039/d2dt02175g

DO - 10.1039/d2dt02175g

M3 - 文章

C2 - 36047681

AN - SCOPUS:85138634297

SN - 1477-9226

VL - 51

SP - 14150

EP - 14155

JO - Dalton Transactions

JF - Dalton Transactions

IS - 37

ER -

Distinct modes of Si-H binding to Rh in complexes of a phosphine-diarylamido-silane (SiNP) pincer ligand

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