N-heterocyclic silyl pincer ligands

Lily S.H. Dixon; Anthony F. Hill; Arup Sinha; Jas S. Ward

doi:10.1021/om400792j

N-heterocyclic silyl pincer ligands

Lily S.H. Dixon, Anthony F. Hill^*, Arup Sinha, Jas S. Ward

^*Corresponding author for this work

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

41 Citations (Scopus)

Abstract

The reaction of 1,2-C₆H₄(NHCH₂PPh ₂)₂ with chlorosilanes Cl₂SiHR (R = Ph, Cl) affords the benzosiladiazoles RHSi(NCH₂PPh₂) ₂C₆H₄ (R = Ph, 1; Cl, 2). The phenyl derivative 1 undergoes chelate-assisted Si-H activation with [RuPhCl(CO)(PPh ₃)₂] and [RhCl(PPh₃)₃] to afford the structurally characterized silyl pincer complexes [RuCl(CO)(PPh ₃){κ³-P,Si,P′-SiPh(NCH₂PPh ₂)₂C₆H₄}] (3) and [RhHCl(PPh ₃){κ³-P,Si,P′-SiPh(NCH₂PPh ₂)₂C₆H₄}] (4). The reaction of 4 with [Et₂NH₂][S₂CNEt₂] affords the complex [RhH(S₂CNEt₂){κ³-P,Si,P′- SiPh(NCH₂PPh₂)₂C₆H₄}] (5), structural data for which demonstrate a pronounced trans influence for the σ-silyl donor.

Original language	English
Pages (from-to)	653-658
Number of pages	6
Journal	Organometallics
Volume	33
Issue number	3
DOIs	https://doi.org/10.1021/om400792j
Publication status	Published - 10 Feb 2014

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@article{a87bf967c17f49b8be59595a0d46306d,

title = "N-heterocyclic silyl pincer ligands",

abstract = "The reaction of 1,2-C6H4(NHCH2PPh 2)2 with chlorosilanes Cl2SiHR (R = Ph, Cl) affords the benzosiladiazoles RHSi(NCH2PPh2) 2C6H4 (R = Ph, 1; Cl, 2). The phenyl derivative 1 undergoes chelate-assisted Si-H activation with [RuPhCl(CO)(PPh 3)2] and [RhCl(PPh3)3] to afford the structurally characterized silyl pincer complexes [RuCl(CO)(PPh 3){κ3-P,Si,P′-SiPh(NCH2PPh 2)2C6H4}] (3) and [RhHCl(PPh 3){κ3-P,Si,P′-SiPh(NCH2PPh 2)2C6H4}] (4). The reaction of 4 with [Et2NH2][S2CNEt2] affords the complex [RhH(S2CNEt2){κ3-P,Si,P′- SiPh(NCH2PPh2)2C6H4}] (5), structural data for which demonstrate a pronounced trans influence for the σ-silyl donor.",

author = "Dixon, {Lily S.H.} and Hill, {Anthony F.} and Arup Sinha and Ward, {Jas S.}",

year = "2014",

month = feb,

day = "10",

doi = "10.1021/om400792j",

language = "English",

volume = "33",

pages = "653--658",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

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T1 - N-heterocyclic silyl pincer ligands

AU - Dixon, Lily S.H.

AU - Hill, Anthony F.

AU - Sinha, Arup

AU - Ward, Jas S.

PY - 2014/2/10

Y1 - 2014/2/10

N2 - The reaction of 1,2-C6H4(NHCH2PPh 2)2 with chlorosilanes Cl2SiHR (R = Ph, Cl) affords the benzosiladiazoles RHSi(NCH2PPh2) 2C6H4 (R = Ph, 1; Cl, 2). The phenyl derivative 1 undergoes chelate-assisted Si-H activation with [RuPhCl(CO)(PPh 3)2] and [RhCl(PPh3)3] to afford the structurally characterized silyl pincer complexes [RuCl(CO)(PPh 3){κ3-P,Si,P′-SiPh(NCH2PPh 2)2C6H4}] (3) and [RhHCl(PPh 3){κ3-P,Si,P′-SiPh(NCH2PPh 2)2C6H4}] (4). The reaction of 4 with [Et2NH2][S2CNEt2] affords the complex [RhH(S2CNEt2){κ3-P,Si,P′- SiPh(NCH2PPh2)2C6H4}] (5), structural data for which demonstrate a pronounced trans influence for the σ-silyl donor.

AB - The reaction of 1,2-C6H4(NHCH2PPh 2)2 with chlorosilanes Cl2SiHR (R = Ph, Cl) affords the benzosiladiazoles RHSi(NCH2PPh2) 2C6H4 (R = Ph, 1; Cl, 2). The phenyl derivative 1 undergoes chelate-assisted Si-H activation with [RuPhCl(CO)(PPh 3)2] and [RhCl(PPh3)3] to afford the structurally characterized silyl pincer complexes [RuCl(CO)(PPh 3){κ3-P,Si,P′-SiPh(NCH2PPh 2)2C6H4}] (3) and [RhHCl(PPh 3){κ3-P,Si,P′-SiPh(NCH2PPh 2)2C6H4}] (4). The reaction of 4 with [Et2NH2][S2CNEt2] affords the complex [RhH(S2CNEt2){κ3-P,Si,P′- SiPh(NCH2PPh2)2C6H4}] (5), structural data for which demonstrate a pronounced trans influence for the σ-silyl donor.

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U2 - 10.1021/om400792j

DO - 10.1021/om400792j

M3 - Article

SN - 0276-7333

VL - 33

SP - 653

EP - 658

JO - Organometallics

JF - Organometallics

IS - 3

ER -

N-heterocyclic silyl pincer ligands

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