Synthesis of hydride and alkyl compounds containing the Cp*Os(NO) fragment. Crystal structure of [Cp*Os(μ-NO)]2

Julia L. Brumaghim; James G. Priepot; Gregory S. Girolami

doi:10.1021/om980657h

Synthesis of hydride and alkyl compounds containing the CpOs(NO) fragment. Crystal structure of [CpOs(μ-NO)]₂

Julia L. Brumaghim, James G. Priepot, Gregory S. Girolami

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

Abstract

Treatment of the pentamethylcyclopentadienyl (Cp*) compound Cp*Os(NO)Br₂ (1) with NaBH₄ yields the dihydride Cp*Os(NO)H₂. The dihydride loses H₂ over several days in solution to form [Cp*Os(μ-NO)]₂; this dinuclear compound can also be formed directly by reduction of 1 with zinc powder. The X-ray crystal structure of [Cp*Os(μ-NO)]₂ shows that nitrosyl ligands are bridging and that the Os-Os distance is 2.539(1) Å. Compound 1 reacts with MgR₂ to form the monoalkylated products Cp*Os(NO)RBr, where R = Me, CH₂SiMe₃, Ph, or o-Tol. The slow ligand substitution kinetics of this reaction prevent the formation of dialkyls of stoichiometry Cp*Os(NO)R₂, even after long reaction times or when a large excess of alkylating agent is used. Dialkyls such as Cp*Os(NO)Me₂ can, however, be obtained by treatment of Cp*Os(NO)MeBr with silver trifluoromethanesulfonate followed by addition of dimethylmagnesium.

Original language	English (US)
Pages (from-to)	2139-2144
Number of pages	6
Journal	Organometallics
Volume	18
Issue number	11
DOIs	https://doi.org/10.1021/om980657h
State	Published - May 24 1999

ASJC Scopus subject areas

Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry

Online availability

10.1021/om980657h

Library availability

Discover UIUC Full Text

Cite this

@article{2b28c988ee8f4288b6a488c0f4c5b51e,

title = "Synthesis of hydride and alkyl compounds containing the Cp*Os(NO) fragment. Crystal structure of [Cp*Os(μ-NO)]2",

abstract = "Treatment of the pentamethylcyclopentadienyl (Cp*) compound Cp*Os(NO)Br2 (1) with NaBH4 yields the dihydride Cp*Os(NO)H2. The dihydride loses H2 over several days in solution to form [Cp*Os(μ-NO)]2; this dinuclear compound can also be formed directly by reduction of 1 with zinc powder. The X-ray crystal structure of [Cp*Os(μ-NO)]2 shows that nitrosyl ligands are bridging and that the Os-Os distance is 2.539(1) {\AA}. Compound 1 reacts with MgR2 to form the monoalkylated products Cp*Os(NO)RBr, where R = Me, CH2SiMe3, Ph, or o-Tol. The slow ligand substitution kinetics of this reaction prevent the formation of dialkyls of stoichiometry Cp*Os(NO)R2, even after long reaction times or when a large excess of alkylating agent is used. Dialkyls such as Cp*Os(NO)Me2 can, however, be obtained by treatment of Cp*Os(NO)MeBr with silver trifluoromethanesulfonate followed by addition of dimethylmagnesium.",

author = "Brumaghim, {Julia L.} and Priepot, {James G.} and Girolami, {Gregory S.}",

year = "1999",

month = may,

day = "24",

doi = "10.1021/om980657h",

language = "English (US)",

volume = "18",

pages = "2139--2144",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "11",

}

TY - JOUR

T1 - Synthesis of hydride and alkyl compounds containing the Cp*Os(NO) fragment. Crystal structure of [Cp*Os(μ-NO)]2

AU - Brumaghim, Julia L.

AU - Priepot, James G.

AU - Girolami, Gregory S.

PY - 1999/5/24

Y1 - 1999/5/24

N2 - Treatment of the pentamethylcyclopentadienyl (Cp*) compound Cp*Os(NO)Br2 (1) with NaBH4 yields the dihydride Cp*Os(NO)H2. The dihydride loses H2 over several days in solution to form [Cp*Os(μ-NO)]2; this dinuclear compound can also be formed directly by reduction of 1 with zinc powder. The X-ray crystal structure of [Cp*Os(μ-NO)]2 shows that nitrosyl ligands are bridging and that the Os-Os distance is 2.539(1) Å. Compound 1 reacts with MgR2 to form the monoalkylated products Cp*Os(NO)RBr, where R = Me, CH2SiMe3, Ph, or o-Tol. The slow ligand substitution kinetics of this reaction prevent the formation of dialkyls of stoichiometry Cp*Os(NO)R2, even after long reaction times or when a large excess of alkylating agent is used. Dialkyls such as Cp*Os(NO)Me2 can, however, be obtained by treatment of Cp*Os(NO)MeBr with silver trifluoromethanesulfonate followed by addition of dimethylmagnesium.

AB - Treatment of the pentamethylcyclopentadienyl (Cp*) compound Cp*Os(NO)Br2 (1) with NaBH4 yields the dihydride Cp*Os(NO)H2. The dihydride loses H2 over several days in solution to form [Cp*Os(μ-NO)]2; this dinuclear compound can also be formed directly by reduction of 1 with zinc powder. The X-ray crystal structure of [Cp*Os(μ-NO)]2 shows that nitrosyl ligands are bridging and that the Os-Os distance is 2.539(1) Å. Compound 1 reacts with MgR2 to form the monoalkylated products Cp*Os(NO)RBr, where R = Me, CH2SiMe3, Ph, or o-Tol. The slow ligand substitution kinetics of this reaction prevent the formation of dialkyls of stoichiometry Cp*Os(NO)R2, even after long reaction times or when a large excess of alkylating agent is used. Dialkyls such as Cp*Os(NO)Me2 can, however, be obtained by treatment of Cp*Os(NO)MeBr with silver trifluoromethanesulfonate followed by addition of dimethylmagnesium.

UR - http://www.scopus.com/inward/record.url?scp=0000015031&partnerID=8YFLogxK

UR - http://www.scopus.com/inward/citedby.url?scp=0000015031&partnerID=8YFLogxK

U2 - 10.1021/om980657h

DO - 10.1021/om980657h

M3 - Article

AN - SCOPUS:0000015031

SN - 0276-7333

VL - 18

SP - 2139

EP - 2144

JO - Organometallics

JF - Organometallics

IS - 11

ER -