Synthesis and characterization of osmium(IV) polyhydride complexes of stoichiometry (C 5Me 5)OsH 3(L). Crystal structures of (C 5Me 5)OsH 3(AsPh 3) and (C 5Me 5)OsH 3(PPha)

Christopher L. Gross; Gregory S. Girolami

doi:10.1021/om060463z

Synthesis and characterization of osmium(IV) polyhydride complexes of stoichiometry (C ₅Me ₅)OsH ₃(L). Crystal structures of (C ₅Me ₅)OsH ₃(AsPh ₃) and (C ₅Me ₅)OsH ₃(PPha)

Christopher L. Gross, Gregory S. Girolami

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

Abstract

Addition of Lewis bases to solutions of (C ₅Me ₅) ₂Os ₂Br ₄ in ethanol affords mononuclear osmium(III) complexes with the general formula (C ₅Me ₅)OsBr ₂(L), where L is AsPh ₃, PPh ₃, P(c-Hx) ₃, PEt ₃, pyridine, or tetrahydrothiophene. These paramagnetic complexes react with sodium borohydride in ethanol to afford the osmium(IV) trihydrides (C ₅Me ₅)OsH ₃(L), where L is AsPh ₃, PPh ₃, P(c-Hx)3, or PEt ₃. X-ray diffraction and NMR studies of the trihydride complexes show that they adopt classical structures (i.e., lacking molecular dihydrogen ligands). Unlike their ruthenium analogues, these osmium(IV) trihydrides show no evidence of quantum tunneling phenomena, probably because the H-Os-H bending motion is characterized by a steep potential energy well.

Original language	English (US)
Pages (from-to)	4792-4798
Number of pages	7
Journal	Organometallics
Volume	25
Issue number	20
DOIs	https://doi.org/10.1021/om060463z
State	Published - Sep 25 2006

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

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title = "Synthesis and characterization of osmium(IV) polyhydride complexes of stoichiometry (C 5Me 5)OsH 3(L). Crystal structures of (C 5Me 5)OsH 3(AsPh 3) and (C 5Me 5)OsH 3(PPha)",

abstract = "Addition of Lewis bases to solutions of (C 5Me 5) 2Os 2Br 4 in ethanol affords mononuclear osmium(III) complexes with the general formula (C 5Me 5)OsBr 2(L), where L is AsPh 3, PPh 3, P(c-Hx) 3, PEt 3, pyridine, or tetrahydrothiophene. These paramagnetic complexes react with sodium borohydride in ethanol to afford the osmium(IV) trihydrides (C 5Me 5)OsH 3(L), where L is AsPh 3, PPh 3, P(c-Hx)3, or PEt 3. X-ray diffraction and NMR studies of the trihydride complexes show that they adopt classical structures (i.e., lacking molecular dihydrogen ligands). Unlike their ruthenium analogues, these osmium(IV) trihydrides show no evidence of quantum tunneling phenomena, probably because the H-Os-H bending motion is characterized by a steep potential energy well.",

author = "Gross, {Christopher L.} and Girolami, {Gregory S.}",

year = "2006",

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doi = "10.1021/om060463z",

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publisher = "American Chemical Society",

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T1 - Synthesis and characterization of osmium(IV) polyhydride complexes of stoichiometry (C 5Me 5)OsH 3(L). Crystal structures of (C 5Me 5)OsH 3(AsPh 3) and (C 5Me 5)OsH 3(PPha)

AU - Gross, Christopher L.

AU - Girolami, Gregory S.

PY - 2006/9/25

Y1 - 2006/9/25

N2 - Addition of Lewis bases to solutions of (C 5Me 5) 2Os 2Br 4 in ethanol affords mononuclear osmium(III) complexes with the general formula (C 5Me 5)OsBr 2(L), where L is AsPh 3, PPh 3, P(c-Hx) 3, PEt 3, pyridine, or tetrahydrothiophene. These paramagnetic complexes react with sodium borohydride in ethanol to afford the osmium(IV) trihydrides (C 5Me 5)OsH 3(L), where L is AsPh 3, PPh 3, P(c-Hx)3, or PEt 3. X-ray diffraction and NMR studies of the trihydride complexes show that they adopt classical structures (i.e., lacking molecular dihydrogen ligands). Unlike their ruthenium analogues, these osmium(IV) trihydrides show no evidence of quantum tunneling phenomena, probably because the H-Os-H bending motion is characterized by a steep potential energy well.

AB - Addition of Lewis bases to solutions of (C 5Me 5) 2Os 2Br 4 in ethanol affords mononuclear osmium(III) complexes with the general formula (C 5Me 5)OsBr 2(L), where L is AsPh 3, PPh 3, P(c-Hx) 3, PEt 3, pyridine, or tetrahydrothiophene. These paramagnetic complexes react with sodium borohydride in ethanol to afford the osmium(IV) trihydrides (C 5Me 5)OsH 3(L), where L is AsPh 3, PPh 3, P(c-Hx)3, or PEt 3. X-ray diffraction and NMR studies of the trihydride complexes show that they adopt classical structures (i.e., lacking molecular dihydrogen ligands). Unlike their ruthenium analogues, these osmium(IV) trihydrides show no evidence of quantum tunneling phenomena, probably because the H-Os-H bending motion is characterized by a steep potential energy well.

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