NDLI: Synthesis of η2-cyclooctene iridium and rhodium complexes supported by a novel P,N-chelate ligand and their reactivity toward hydrosilanes: facile Cl migration from metal to silicon via silylene complex intermediates and formation of a base-stabilised silylene complex

Please wait, while we are loading the content...

The gas-phase structure and some reactions of the bulky primary silane (Me₃Si)₃CSiH₃ and the solid-state structure of the bulky dialkyl disilane [(Me₃Si)₃CSiH₂]₂

Enzyme mediated silicon–oxygen bond formation; the use of Rhizopus oryzae lipase, lysozyme and phytase under mild conditions

Rapid assembly of explicit, functional silicones

Unsuccessful attempts to add alcohols to transient 2-amino-2-siloxy-silenes - leading to a new benign route for base-free alcohol protection

Synthesis of η²-cyclooctene iridium and rhodium complexes supported by a novel P,N-chelate ligand and their reactivity toward hydrosilanes: facile Cl migration from metal to silicon via silylene complex intermediates and formation of a base-stabilised silylene complex

Novel neutral hexacoordinate silicon(iv) complexes with two bidentate monoanionic benzamidinato ligands

Synthesis and structures of (dialkylsilylene)bis(phosphine)-nickel, palladium, and platinum complexes and (η⁶-arene)(dialkylsilylene)nickel complexes

Synthesis and properties of 5,10,15,20-tetrakis[4-(alkoxysilyl)phenyl]porphyrins: an application of selective deprotection of benzaldehyde diethyl acetals in the presence of alkoxysilyl groups

Back cover

Dalton Transactions Vol - 39 Issue - 29

Dalton Transactions Vol - 39 Issue - 19

Dalton Transactions Vol - 39 Issue - 9

Dalton Transactions Vol - 39 Issue - 8

Dalton Transactions Vol - 39 Issue - 7

Dalton Transactions Vol - 39 Issue - 6

Dalton Transactions Vol - 39 Issue - 5

Dalton Transactions Vol -0

Synthesis of η²-cyclooctene iridium and rhodium complexes supported by a novel P,N-chelate ligand and their reactivity toward hydrosilanes: facile Cl migration from metal to silicon via silylene complex intermediates and formation of a base-stabilised silylene complex

Content Provider	Royal Society of Chemistry (RSC)
Author	Tobita, Hiromi Hashimoto, Hisako Suzuki, Toshinori
Copyright Year	2010
Abstract	η2-Cyclooctene iridium and rhodium complexes bearing a P,N-chelate ligand C6H3Me-3-PCy2-4-NMe2 (abbreviated as PcyN), (PcyN-P,N)MCl(η2-coe) (1: M = Ir, 2: M = Rh), were synthesised and reactions toward several sterically hindered hydrosilanes were investigated to clarify their reactivity. The reaction of 1 with H2SiMes2 (Mes = mesityl = 2,4,6-trimethylphenyl) proceeded at 40 °C to give a di-iridium complex bridged by a chlorosilylene ligand (PcyN-P,N)2Ir2H2(μ-Cl)(μ-H)(μ-SiClMes) (5). The reaction of 1 with HSiMe2SiMes2Me occurred at room temperature to afford HSiMesMe2 and a silyl complex 6 formed by metallation of an ortho-methyl group of Mes, which slowly dimerised to give a dinuclear complex containing a chlorosilyl ligand (PcyN-P,N)2Ir2H(μ-Cl)(μ-H)[μ-SiMeCl(C6H3-2,4-Me2-6-CH)-Si,C,C] (7). The formation of complexes 5, 6 and 7 suggests that facile migration of Cl from Ir to Si occurs probably via silylene iridium intermediates. Treatment of 1 with HSiMe2SiMe2OMe at room temperature yielded a methoxy-bridged bis(silylene) complex (PcyN-P,N)IrHCl[SiMe2··O(Me)··SiMe2-Si,Si] (8) quantitatively, whose X-ray crystal structure was determined as the first iridium complex of this type. The reactions of 1 and 2 with a bulky trihydrosilane H3SiC(SiMe3)3 underwent an intramolecular γ-Si–Me activation to afford (PcyN-P,N)MHn[SiMe2C(SiMe3)2SiClMe-Si,Si] (9: M = Ir, n = 3; 10: M = Rh, n = 1). Complex 1 even reacted with an extremely sterically hindered terphenylhydrosilane H3SiDmp (Dmp = 2,6-dimesitylphenyl) in the presence of PMe3 to give a chlorosilyl complex (PcyN-P,N)IrH2(PMe3)(SiHClDmp) (11) without intramolecular bond activation. Complex 1 also reacted with H3SiTrip (Trip = 2,4,6-triisopropylphenyl) in the presence of excess 4-(dimethylamino)pyridine (DMAP) at room temperature to give a chlorido(dihydrosilyl) complex (PcyN-P,N)IrHCl(DMAP)(SiH2Trip) (12) instantaneously. Treatment of complex 12 with LiB(C6F5)4·2.5Et2O provided a cationic DMAP-stabilised silylene complex [(PcyN-P,N))IrH2(DMAP)(SiHTrip ← DMAP)][B(C6F5)4] (13).
Starting Page	9386
Ending Page	9400
Page Count	15
File Format	HTM / HTML PDF
ISSN	14779226
Volume Number	39
Issue Number	39
Journal	Dalton Transactions
DOI	10.1039/c0dt00264j
Language	English
Publisher	Royal Society of Chemistry
Access Restriction	Open
Subject Keyword	Cyclooctene Iridium Rhodium Ligand NME2 Mesitylene Silylene X-ray crystallography Chemical bond 4-Dimethylaminopyridine
Content Type	Text
Resource Type	Article
Subject	Inorganic Chemistry

Sl.	Authority	Responsibilities	Communication Details
1	Ministry of Education (GoI), Department of Higher Education	Sanctioning Authority	https://www.education.gov.in/ict-initiatives
2	Indian Institute of Technology Kharagpur	Host Institute of the Project: The host institute of the project is responsible for providing infrastructure support and hosting the project	https://www.iitkgp.ac.in
3	National Digital Library of India Office, Indian Institute of Technology Kharagpur	The administrative and infrastructural headquarters of the project	Dr. B. Sutradhar bsutra@ndl.gov.in
4	Project PI / Joint PI	Principal Investigator and Joint Principal Investigators of the project	Dr. B. Sutradhar bsutra@ndl.gov.in Prof. Saswat Chakrabarti will be added soon
5	Website/Portal (Helpdesk)	Queries regarding NDLI and its services	support@ndl.gov.in
6	Contents and Copyright Issues	Queries related to content curation and copyright issues	content@ndl.gov.in
7	National Digital Library of India Club (NDLI Club)	Queries related to NDLI Club formation, support, user awareness program, seminar/symposium, collaboration, social media, promotion, and outreach	clubsupport@ndl.gov.in
8	Digital Preservation Centre (DPC)	Assistance with digitizing and archiving copyright-free printed books	dpc@ndl.gov.in
9	IDR Setup or Support	Queries related to establishment and support of Institutional Digital Repository (IDR) and IDR workshops	idr@ndl.gov.in

N-Heterocyclic Silylene (NHSi) Rhodium and Iridium Complexes: Synthesis, Structure, Reactivity, and Catalytic Ability

Di-μ-chlorido-bis[bis(η2-cyclooctene)iridium(I)]

Synthesis and reactivity of rhodium and iridium alkene, alkyl and silyl complexes supported by a phenyl-substituted PNP pincer ligand

Electrochemical Properties of (η5-C5Me5)–Rhodium and – Iridium Complexes Containing Bis(pyrazolyl)alkane Ligands (2014)

Facile synthesis of rhodium and iridium complexes bearing a [PEP]-type ligand (E = Ge or Sn) via E–C bond cleavage

A Genuine Stannylone with a Monoatomic Two-Coordinate Tin(0) Atom Supported by a Bis(silylene) Ligand.

Reversible intramolecular base-stabilization in silylene (silanediyl) complexes: surprising reactivity for silylene coordination compounds with a dynamic N.cntdot..cntdot..cntdot.Si.cntdot..cntdot..cntdot.N bond

Rhodium and Iridium Pincer Complexes Supported by Bis(phosphino)silyl Ligation: Applications in Bond Cleavage Chemistry

Iridium Complexes of the Conformationally Rigid IBioxMe4 Ligand: Hydride Complexes and Dehydrogenation of Cyclooctene

Synthesis of η²-cyclooctene iridium and rhodium complexes supported by a novel P,N-chelate ligand and their reactivity toward hydrosilanes: facile Cl migration from metal to silicon via silylene complex intermediates and formation of a base-stabilised silylene complex

Similar Documents

N-Heterocyclic Silylene (NHSi) Rhodium and Iridium Complexes: Synthesis, Structure, Reactivity, and Catalytic Ability

Di-μ-chlorido-bis[bis(η2-cyclooctene)iridium(I)]

Synthesis and reactivity of rhodium and iridium alkene, alkyl and silyl complexes supported by a phenyl-substituted PNP pincer ligand

Electrochemical Properties of (η5-C5Me5)–Rhodium and – Iridium Complexes Containing Bis(pyrazolyl)alkane Ligands (2014)

Facile synthesis of rhodium and iridium complexes bearing a [PEP]-type ligand (E = Ge or Sn) via E–C bond cleavage

A Genuine Stannylone with a Monoatomic Two-Coordinate Tin(0) Atom Supported by a Bis(silylene) Ligand.

Reversible intramolecular base-stabilization in silylene (silanediyl) complexes: surprising reactivity for silylene coordination compounds with a dynamic N.cntdot..cntdot..cntdot.Si.cntdot..cntdot..cntdot.N bond

Rhodium and Iridium Pincer Complexes Supported by Bis(phosphino)silyl Ligation: Applications in Bond Cleavage Chemistry

Iridium Complexes of the Conformationally Rigid IBioxMe4 Ligand: Hydride Complexes and Dehydrogenation of Cyclooctene

Synthesis of η2-cyclooctene iridium and rhodium complexes supported by a novel P,N-chelate ligand and their reactivity toward hydrosilanes: facile Cl migration from metal to silicon via silylene complex intermediates and formation of a base-stabilised silylene complex

Synthesis of η²-cyclooctene iridium and rhodium complexes supported by a novel P,N-chelate ligand and their reactivity toward hydrosilanes: facile Cl migration from metal to silicon via silylene complex intermediates and formation of a base-stabilised silylene complex