New tridentate phosphine rhodium and iridium complexes, including a stable rhodium(I) silyl. Si-S activation and a strong effect of X in (PP2)M-X (X = H, Cl, Me) on Si-H activation

Roman Goikhman, Michael Aizenberg, Yehoshoa Ben-David, Linda J W Shimon, David Milstein

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Abstract

Rhodium and iridium complexes of the general formula (PP2)MX bearing the new triphosphine ligand iPr2P(CH2)3P(Ph)(CH2) 3PiPr2 (PP2) have been synthesized. Reactivity of the PP2MX complexes toward HSi(SEt)3 was studied. Whereas (PP2)RhCl and (PP2)IrCl do not react with HSi(SEt)3, (PP2)RhH gives rise to the Rh(III) adduct [(PP2)Rh(H)2Si(SEt)3], and (PP2)RhMe (3) activates both the Si-H and the Si-S bonds of HSi(SEt)3, affording the Rh(I) complexes (PP2)RhSi(SEt)3 (5) and (PP2)RhSEt (6). Only a few stable Rh(I) silyl complexes are known, and Si-S bond activation by transition-metal complexes has been rarely observed. The X-ray crystal structure of 5 exhibits a considerable distortion from square-planar geometry, the average angle between the trans-disposed ligands being 152.5°. In contrast to 3, (PP2)IrMe (8) forms a stable Ir(III) adduct with HSi(SEt)3, fac-[(PP2)Ir-(Me)(H)(Si(SEt)3)] (9). No Si-S activation was observed with 8. Thus, the reactivity of (PP2)-MX complexes toward HSi(SEt)3 strongly depends on the nature of M and X.

Original languageEnglish
Pages (from-to)5060-5065
Number of pages6
JournalOrganometallics
Volume21
Issue number23
DOIs
Publication statusPublished - Nov 11 2002

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phosphine
Iridium
Rhodium
iridium
rhodium
phosphines
adducts
Bearings (structural)
reactivity
Chemical activation
activation
Ligands
ligands
Coordination Complexes
Transition metals
Crystal structure
transition metals
X rays
crystal structure
Geometry

ASJC Scopus subject areas

  • Inorganic Chemistry
  • Organic Chemistry

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New tridentate phosphine rhodium and iridium complexes, including a stable rhodium(I) silyl. Si-S activation and a strong effect of X in (PP2)M-X (X = H, Cl, Me) on Si-H activation. / Goikhman, Roman; Aizenberg, Michael; Ben-David, Yehoshoa; Shimon, Linda J W; Milstein, David.

In: Organometallics, Vol. 21, No. 23, 11.11.2002, p. 5060-5065.

Research output: Contribution to journalArticle

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abstract = "Rhodium and iridium complexes of the general formula (PP2)MX bearing the new triphosphine ligand iPr2P(CH2)3P(Ph)(CH2) 3PiPr2 (PP2) have been synthesized. Reactivity of the PP2MX complexes toward HSi(SEt)3 was studied. Whereas (PP2)RhCl and (PP2)IrCl do not react with HSi(SEt)3, (PP2)RhH gives rise to the Rh(III) adduct [(PP2)Rh(H)2Si(SEt)3], and (PP2)RhMe (3) activates both the Si-H and the Si-S bonds of HSi(SEt)3, affording the Rh(I) complexes (PP2)RhSi(SEt)3 (5) and (PP2)RhSEt (6). Only a few stable Rh(I) silyl complexes are known, and Si-S bond activation by transition-metal complexes has been rarely observed. The X-ray crystal structure of 5 exhibits a considerable distortion from square-planar geometry, the average angle between the trans-disposed ligands being 152.5°. In contrast to 3, (PP2)IrMe (8) forms a stable Ir(III) adduct with HSi(SEt)3, fac-[(PP2)Ir-(Me)(H)(Si(SEt)3)] (9). No Si-S activation was observed with 8. Thus, the reactivity of (PP2)-MX complexes toward HSi(SEt)3 strongly depends on the nature of M and X.",
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T1 - New tridentate phosphine rhodium and iridium complexes, including a stable rhodium(I) silyl. Si-S activation and a strong effect of X in (PP2)M-X (X = H, Cl, Me) on Si-H activation

AU - Goikhman, Roman

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N2 - Rhodium and iridium complexes of the general formula (PP2)MX bearing the new triphosphine ligand iPr2P(CH2)3P(Ph)(CH2) 3PiPr2 (PP2) have been synthesized. Reactivity of the PP2MX complexes toward HSi(SEt)3 was studied. Whereas (PP2)RhCl and (PP2)IrCl do not react with HSi(SEt)3, (PP2)RhH gives rise to the Rh(III) adduct [(PP2)Rh(H)2Si(SEt)3], and (PP2)RhMe (3) activates both the Si-H and the Si-S bonds of HSi(SEt)3, affording the Rh(I) complexes (PP2)RhSi(SEt)3 (5) and (PP2)RhSEt (6). Only a few stable Rh(I) silyl complexes are known, and Si-S bond activation by transition-metal complexes has been rarely observed. The X-ray crystal structure of 5 exhibits a considerable distortion from square-planar geometry, the average angle between the trans-disposed ligands being 152.5°. In contrast to 3, (PP2)IrMe (8) forms a stable Ir(III) adduct with HSi(SEt)3, fac-[(PP2)Ir-(Me)(H)(Si(SEt)3)] (9). No Si-S activation was observed with 8. Thus, the reactivity of (PP2)-MX complexes toward HSi(SEt)3 strongly depends on the nature of M and X.

AB - Rhodium and iridium complexes of the general formula (PP2)MX bearing the new triphosphine ligand iPr2P(CH2)3P(Ph)(CH2) 3PiPr2 (PP2) have been synthesized. Reactivity of the PP2MX complexes toward HSi(SEt)3 was studied. Whereas (PP2)RhCl and (PP2)IrCl do not react with HSi(SEt)3, (PP2)RhH gives rise to the Rh(III) adduct [(PP2)Rh(H)2Si(SEt)3], and (PP2)RhMe (3) activates both the Si-H and the Si-S bonds of HSi(SEt)3, affording the Rh(I) complexes (PP2)RhSi(SEt)3 (5) and (PP2)RhSEt (6). Only a few stable Rh(I) silyl complexes are known, and Si-S bond activation by transition-metal complexes has been rarely observed. The X-ray crystal structure of 5 exhibits a considerable distortion from square-planar geometry, the average angle between the trans-disposed ligands being 152.5°. In contrast to 3, (PP2)IrMe (8) forms a stable Ir(III) adduct with HSi(SEt)3, fac-[(PP2)Ir-(Me)(H)(Si(SEt)3)] (9). No Si-S activation was observed with 8. Thus, the reactivity of (PP2)-MX complexes toward HSi(SEt)3 strongly depends on the nature of M and X.

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