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Hydrido(carbene), Hydrido(diazoalkane), Aqua(carbene), and Vinyl(carbene) Complexes of Osmium(II)
Author(s) -
Werner Helmut,
Stüer Wolfram,
Wolf Justin,
Laubender Matthias,
Weberndörfer Birgit,
HerbstIrmer Regine,
Lehmann Christopher
Publication year - 1999
Publication title -
european journal of inorganic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 1434-1948
DOI - 10.1002/(sici)1099-0682(199911)1999:11<1889::aid-ejic1889>3.0.co;2-z
Subject(s) - carbene , chemistry , osmium , medicinal chemistry , stereochemistry , ether , crystallography , ruthenium , catalysis , organic chemistry
The five‐coordinate compound [OsHCl(CO)(P i Pr 3 ) 2 ] ( 1 ) reacts with CH 2 N 2 and other diazoalkanes RCHN 2 (R = Ph, CO 2 Et, SiMe 3 ) in ether or toluene at 25 °C to give instead of the expected insertion products [Os(CH 2 R)Cl(CO)(P i Pr 3 ) 2 ] the isomeric hydrido(carbene)osmium(II) complexes [OsHCl(=CHR)(CO)(P i Pr 3 ) 2 ] ( 2–5 ) in excellent yields. With Me 3 SiCHN 2 as the substrate, the 1:1 adduct [OsHCl(N 2 CHSiMe 3 )(CO)(P i Pr 3 ) 2 ] ( 6 ) was detected at low temperature as an intermediate. The reactions of 1 with Ph 2 CN 2 and Cl 4 C 5 N 2 afford the hydrido(diazoalkane)compounds [OsHCl(N 2 CR 2 )(CO)(P i Pr 3 ) 2 ] ( 7 , 8 ), which are quite stable and do not eliminate N 2 to give the corresponding hydrido(carbene)metal derivatives. Treatment of 3 (R = Ph) with either HCl or HBF 4 /H 2 O leads to the cleavage of the Os‐H bond and results in the formation of [OsCl 2 (=CHPh)(CO)(P i Pr 3 ) 2 ] ( 10 ) and [OsCl(=CHPh)(OH 2 )(CO)(P i Pr 3 ) 2 ]BF 4 ( 11 ), respectively. The vinyl compound [OsCl(CH=CHPh)(CO)(P i Pr 3 ) 2 ] ( 12 ) behaves similarly to 1 and affords the carbene complex [OsCl(CH=CHPh)(=CHPh)(CO)(P i Pr 3 ) 2 ] ( 13 ) upon treatment with PhCHN 2 . Compound 13 rearranges in solution at room temperature to give the π‐allyl complex [Os(η 3 ‐PhCHCHCHPh)Cl(CO)(P i Pr 3 ) 2 ] ( 14 ) as the dominating species. The crystal and molecular structures of 4 , 5 , 10 , and 11 have been determined by X‐ray crystallography.