Rh(I) and Rh(III) silyl PMe3 complexes. Syntheses, reactions and 103Rh NMR spectroscopy

Michael Aizenberg, Juergen Ott, Cornelis J. Elsevier, David Milstein

Research output: Contribution to journalArticle

33 Citations (Scopus)

Abstract

Synthetic approaches to Rh(I) silyls are described. The complexes LnRhSiR3 (L=PMe3; 6, n=4, R3=(OEt)3; 7, n=4, R3=Me(OMe)2; 21, n=3, R3=Ph3) resulted from the reactions of MeRhL4 (1) with the corresponding silanes HSiR3. Complex 21 was prepared alternatively from PhRhL3 (2) and HSiPh3, while analogous reactions of HSi(OEt)3, HSiMe(OMe)2 and HSi(OMe)3 led to the bis(silyl)hydrides fac-L3Rh(SiR3)2(H) (8, R3=(OEt)3; 9, R3=Me(OMe)2; 13, R3=(OMe)3). Like in analogous iridium-based systems, the outcome of these reactions largely depends on the nature of substituents at the silicon atom. Synthesis of Rh(I) silyls inaccessible by this route, namely those with alkyl substituents at the silicon, LnRhSiR3 (19, n=3, R3=PhMe2; 22, n=4, R3=Me3), was achieved utilizing nucleophilic attack of the corresponding silyllithiums at [L4Rh]Cl. The solid-state structure of 19 was determined by X-ray crystallography. C17H38P3SiRh, Fw=466.38 monoclinic, C2/m, a=13.304(3) Å, b=13.814(2) Å, c=13.123(4) Å, β=110.66(3) deg, V=2257(1) Å3, Z=4, dcalcd=1.373 g cm-3, μ=1.019 mm-1. A series of di(hydrido)silyls fac-L3Rh(H)2(SiR3) (10, R3=(OEt)3; 15, R3=PhMe2; 16, R3=Ph3) was synthesized using oxidative additions of HSiR3 to HRhL4 (3). Complexes 10, 15, 16 are thermodynamically stable with respect to H-H and Si-H reductive-elimination reactions at ambient conditions. Complex 8 reductively eliminates HSi(OEt)3 reversibly at room temperature and complex 13 is capable upon heating of mediating dehydrogenative Si-Si coupling of HSi(OMe)3 and redistribution of [(MeO)3Si]2. 103Rh NMR data obtained for MeRhL4 (1), HRhL4 (3), L3RhSiPhMe2 (19), L3RhSiPh3 (21) and for the di(hydrido) silyls (10, 15, 16) allowed to qualitatively evaluate steric and electronic effects of methyl, silyl, and hydride ligands on the 103Rh chemical shift.

Original languageEnglish
Pages (from-to)81-92
Number of pages12
JournalJournal of Organometallic Chemistry
Volume551
Issue number1-2
Publication statusPublished - Jan 30 1998

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Silicon
Hydrides
Nuclear magnetic resonance spectroscopy
Magnetic Resonance Spectroscopy
Silanes
Iridium
nuclear magnetic resonance
X ray crystallography
X Ray Crystallography
Chemical shift
synthesis
Heating
spectroscopy
hydrides
Ligands
Nuclear magnetic resonance
Atoms
Hydrogen
Temperature
silicon

Keywords

  • Comlexes
  • NMR spectroscopy
  • Silyls

ASJC Scopus subject areas

  • Biochemistry
  • Inorganic Chemistry
  • Organic Chemistry
  • Physical and Theoretical Chemistry
  • Materials Chemistry

Cite this

Rh(I) and Rh(III) silyl PMe3 complexes. Syntheses, reactions and 103Rh NMR spectroscopy. / Aizenberg, Michael; Ott, Juergen; Elsevier, Cornelis J.; Milstein, David.

In: Journal of Organometallic Chemistry, Vol. 551, No. 1-2, 30.01.1998, p. 81-92.

Research output: Contribution to journalArticle

Aizenberg, Michael ; Ott, Juergen ; Elsevier, Cornelis J. ; Milstein, David. / Rh(I) and Rh(III) silyl PMe3 complexes. Syntheses, reactions and 103Rh NMR spectroscopy. In: Journal of Organometallic Chemistry. 1998 ; Vol. 551, No. 1-2. pp. 81-92.
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abstract = "Synthetic approaches to Rh(I) silyls are described. The complexes LnRhSiR3 (L=PMe3; 6, n=4, R3=(OEt)3; 7, n=4, R3=Me(OMe)2; 21, n=3, R3=Ph3) resulted from the reactions of MeRhL4 (1) with the corresponding silanes HSiR3. Complex 21 was prepared alternatively from PhRhL3 (2) and HSiPh3, while analogous reactions of HSi(OEt)3, HSiMe(OMe)2 and HSi(OMe)3 led to the bis(silyl)hydrides fac-L3Rh(SiR3)2(H) (8, R3=(OEt)3; 9, R3=Me(OMe)2; 13, R3=(OMe)3). Like in analogous iridium-based systems, the outcome of these reactions largely depends on the nature of substituents at the silicon atom. Synthesis of Rh(I) silyls inaccessible by this route, namely those with alkyl substituents at the silicon, LnRhSiR3 (19, n=3, R3=PhMe2; 22, n=4, R3=Me3), was achieved utilizing nucleophilic attack of the corresponding silyllithiums at [L4Rh]Cl. The solid-state structure of 19 was determined by X-ray crystallography. C17H38P3SiRh, Fw=466.38 monoclinic, C2/m, a=13.304(3) {\AA}, b=13.814(2) {\AA}, c=13.123(4) {\AA}, β=110.66(3) deg, V=2257(1) {\AA}3, Z=4, dcalcd=1.373 g cm-3, μ=1.019 mm-1. A series of di(hydrido)silyls fac-L3Rh(H)2(SiR3) (10, R3=(OEt)3; 15, R3=PhMe2; 16, R3=Ph3) was synthesized using oxidative additions of HSiR3 to HRhL4 (3). Complexes 10, 15, 16 are thermodynamically stable with respect to H-H and Si-H reductive-elimination reactions at ambient conditions. Complex 8 reductively eliminates HSi(OEt)3 reversibly at room temperature and complex 13 is capable upon heating of mediating dehydrogenative Si-Si coupling of HSi(OMe)3 and redistribution of [(MeO)3Si]2. 103Rh NMR data obtained for MeRhL4 (1), HRhL4 (3), L3RhSiPhMe2 (19), L3RhSiPh3 (21) and for the di(hydrido) silyls (10, 15, 16) allowed to qualitatively evaluate steric and electronic effects of methyl, silyl, and hydride ligands on the 103Rh chemical shift.",
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TY - JOUR

T1 - Rh(I) and Rh(III) silyl PMe3 complexes. Syntheses, reactions and 103Rh NMR spectroscopy

AU - Aizenberg, Michael

AU - Ott, Juergen

AU - Elsevier, Cornelis J.

AU - Milstein, David

PY - 1998/1/30

Y1 - 1998/1/30

N2 - Synthetic approaches to Rh(I) silyls are described. The complexes LnRhSiR3 (L=PMe3; 6, n=4, R3=(OEt)3; 7, n=4, R3=Me(OMe)2; 21, n=3, R3=Ph3) resulted from the reactions of MeRhL4 (1) with the corresponding silanes HSiR3. Complex 21 was prepared alternatively from PhRhL3 (2) and HSiPh3, while analogous reactions of HSi(OEt)3, HSiMe(OMe)2 and HSi(OMe)3 led to the bis(silyl)hydrides fac-L3Rh(SiR3)2(H) (8, R3=(OEt)3; 9, R3=Me(OMe)2; 13, R3=(OMe)3). Like in analogous iridium-based systems, the outcome of these reactions largely depends on the nature of substituents at the silicon atom. Synthesis of Rh(I) silyls inaccessible by this route, namely those with alkyl substituents at the silicon, LnRhSiR3 (19, n=3, R3=PhMe2; 22, n=4, R3=Me3), was achieved utilizing nucleophilic attack of the corresponding silyllithiums at [L4Rh]Cl. The solid-state structure of 19 was determined by X-ray crystallography. C17H38P3SiRh, Fw=466.38 monoclinic, C2/m, a=13.304(3) Å, b=13.814(2) Å, c=13.123(4) Å, β=110.66(3) deg, V=2257(1) Å3, Z=4, dcalcd=1.373 g cm-3, μ=1.019 mm-1. A series of di(hydrido)silyls fac-L3Rh(H)2(SiR3) (10, R3=(OEt)3; 15, R3=PhMe2; 16, R3=Ph3) was synthesized using oxidative additions of HSiR3 to HRhL4 (3). Complexes 10, 15, 16 are thermodynamically stable with respect to H-H and Si-H reductive-elimination reactions at ambient conditions. Complex 8 reductively eliminates HSi(OEt)3 reversibly at room temperature and complex 13 is capable upon heating of mediating dehydrogenative Si-Si coupling of HSi(OMe)3 and redistribution of [(MeO)3Si]2. 103Rh NMR data obtained for MeRhL4 (1), HRhL4 (3), L3RhSiPhMe2 (19), L3RhSiPh3 (21) and for the di(hydrido) silyls (10, 15, 16) allowed to qualitatively evaluate steric and electronic effects of methyl, silyl, and hydride ligands on the 103Rh chemical shift.

AB - Synthetic approaches to Rh(I) silyls are described. The complexes LnRhSiR3 (L=PMe3; 6, n=4, R3=(OEt)3; 7, n=4, R3=Me(OMe)2; 21, n=3, R3=Ph3) resulted from the reactions of MeRhL4 (1) with the corresponding silanes HSiR3. Complex 21 was prepared alternatively from PhRhL3 (2) and HSiPh3, while analogous reactions of HSi(OEt)3, HSiMe(OMe)2 and HSi(OMe)3 led to the bis(silyl)hydrides fac-L3Rh(SiR3)2(H) (8, R3=(OEt)3; 9, R3=Me(OMe)2; 13, R3=(OMe)3). Like in analogous iridium-based systems, the outcome of these reactions largely depends on the nature of substituents at the silicon atom. Synthesis of Rh(I) silyls inaccessible by this route, namely those with alkyl substituents at the silicon, LnRhSiR3 (19, n=3, R3=PhMe2; 22, n=4, R3=Me3), was achieved utilizing nucleophilic attack of the corresponding silyllithiums at [L4Rh]Cl. The solid-state structure of 19 was determined by X-ray crystallography. C17H38P3SiRh, Fw=466.38 monoclinic, C2/m, a=13.304(3) Å, b=13.814(2) Å, c=13.123(4) Å, β=110.66(3) deg, V=2257(1) Å3, Z=4, dcalcd=1.373 g cm-3, μ=1.019 mm-1. A series of di(hydrido)silyls fac-L3Rh(H)2(SiR3) (10, R3=(OEt)3; 15, R3=PhMe2; 16, R3=Ph3) was synthesized using oxidative additions of HSiR3 to HRhL4 (3). Complexes 10, 15, 16 are thermodynamically stable with respect to H-H and Si-H reductive-elimination reactions at ambient conditions. Complex 8 reductively eliminates HSi(OEt)3 reversibly at room temperature and complex 13 is capable upon heating of mediating dehydrogenative Si-Si coupling of HSi(OMe)3 and redistribution of [(MeO)3Si]2. 103Rh NMR data obtained for MeRhL4 (1), HRhL4 (3), L3RhSiPhMe2 (19), L3RhSiPh3 (21) and for the di(hydrido) silyls (10, 15, 16) allowed to qualitatively evaluate steric and electronic effects of methyl, silyl, and hydride ligands on the 103Rh chemical shift.

KW - Comlexes

KW - NMR spectroscopy

KW - Silyls

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