Treatment of Os (=CAr-η
2-CH=C=CHAr)CI
2(PPh
3)
2 with Au(C≡CR)(PPh
3)(R = Ph, p-tolyl, n-butyl, SiMe
3) led to the formation of the osmabenzyne complexes OS(≡CCR=C(CH
2Ar)CH=CAr)Cl
2(PPh
3)
2. Treatment of Os(=CPh-η
2-CH=C=CHPh)Cl
2(PPh
3)
2 with PhC≡C-C≡CPh gave the fulvene complex OsCl
2(η
6-C
5H(C≡CPh)(Ph)
2CHPh)(PPh
3).
Reaction of Os(≡CC(SiMe
3)=C(CH
3)C(SiMe
3)=CH)Cl
2(PPh
3)
2 with TlOTf afforded the cationic osmabenzyne [Os(≡CC(SiMe
3)=C(CH
3)C(SiMe
3)=CH)CI(H
2O)(PPh
3)
2]OTf, which can undergo ligand substitution with PMe
3 and 2,2'-bipyridine to produce [Os(≡CC(SiMe
3)=C(CH
3)C(SiMe
3)=CH)Cl(PMe
3)(PPh
3)
2]OTf and [Os(≡CC(SiMe
3)=C(Me)C(SiMe
3)=CH)(bipy)(PPh
3)
2](OTf)
2, respectively.
Treatment of Os(≡CC(SiMe
3)=C(CH
3)C(SiMe
3)=CH)Cl
2(PPh
3)
2 and Os(≡CCH=C(CH
3)CH=CH)CI
2(PPh
3)
2 with bromine produced the same osmabenzyne Os(≡CC(Br)=C(CH
3)C(Br)=CH)Br
2(PPh
3)
2. Nitration of Os(≡CC(SiMe
3)=C(CH
3)C(SiMe
3)=CH)Cl
2(PPh
3)
2 with NO
2BF
4 and NaCl led to Os(≡CC(SiMe
3)=C(CH
3)C(NO
2)=CH)Cl
2(PPh
3)
2, Os(≡CC(SiMe
3)=C(CH
3)C(NO)=CH)CI
2(PPh
3)
2, and a paramagnetic complex. Os(≡CC(SiMe
3)=C(CH
3)C(NO)=CH)CI
2(PPh
3)
2 could also be prepared from the reaction of Os(≡CC(SiMe
3)=C(CH
3)C(SiMe
3)=CH)CI
2(PPh
3)
2 with NOBF
4 and NaCI. Reaction of Os(≡CC(SiMe
3)=C(CH
3)C(SiMe
3)=CH)Cl
2(PPh
3)
2 with AICI
3/H
2O
2 produced Os(η
2=C(O)CCI=C(CH
3)CCI=CH)(PPh
3)
2CI
2 and Os(η
2=C(O)CCI=C(CH
3)C(SiMe
3)=CH)(PPh
3)
2CI
2.
Reaction of osmabenzyne Os(≡CC(SiMe
3)=C(Me)C(SiMe
3)=CH)(bipy)(PPh
3)
2](OTf)
2 with water and methanol produced osmabenzenes [Os(=C(OH)CH=C(CH
3)C(SiMe
3)=CH)(bipy)(PPh
3)
2]OTf and [Os=(C(OMe)CH=C(CH
3)C(SiMe
3)=CH)(bipy)(PPh
3)
2]OTf repectively. The vinyl complex [Os(CH=C(SiMe
3)C(CH
3)=CH
2)(CO)(bipy)(PPh
3)
2]OTf was isolated from the reaction of Os(≡CC(SiMe
3)=C(Me)C(SiMe
3)=CH)(bipy)(PPh
3)
2](OTf)
2 with water. Treatment of Os(≡CC(SiMe
3)=C(Me)C(SiMe
3)=CH)(bipy)(PPh
3)
2](OTf)
2 with NaBH
4 produced the cyclopentadienyl complex [Os(η
5-CHCHC(SiMe
3)C(CH
3)C(SiMe
3))(bipy)(PPh
3)]OTf.
Reaction of mer-[OsCI
3(≡CCH=CPh
2)(PPh
3)
2] and fac-[OsCI
3(≡CCH=CPh
2)(PPh
3)
2] with primary amines RNH
2 (R = CH
3CH
2, CH
3(CH
2)
3) produced the allenylidene complexes cis- or mer-Os(=C=C=CPh
2)CI
2(RNH
2)(PPh
3)
2, respectively (R = CH
3CH
2, CH
3(CH
2)
3). Reaction of mer-[OsCI
3(≡CCH=CPh
2)(PPh
3)
2] with tert-butylamine afforded the indenyl complex Os(η
5C
9H
5(
tBu)(Ph))(PPh
3)
2CI. Treatment of mer-[OsCI
3(≡CCH=CPh
2)(PPh
3)
2] with diethylamine gave a mixture of allenylidene Os(=C=C=CPh
2)CI
2(CH
3CH
2NH
2)(PPh
3)
2 and hydrido-carbyne Os(≡CCH=CPh
2) (PPh
3)
2HCI
2.
Treatment of mer-[OsCI
3(≡CCH=CPh
2)(PPh
3)
2] with the tertiary amine (NH
2CH
2CH
2)
3N gave the cationic carbene complex [Os(η
3-N(CH
2CH
2NH
2)
2CH
2CH
2NH)(=CCH=CPh
2)CI(PPh
3)]CI. Reaction of mer-[OsCI
3(≡CCH=CPh
2)(PPh
3)
2] with pyridine (py) and 4-picoline (pi) under refluxing condition produced the carbyne complexes Os(≡CCH=CPh
2)CI
3(PPh
3)(py) and Os(≡CCH=CPh
2)CI
3(PPh
3)(pi), respectively.
Treatment of mer-[MCI
3(≡CCH=CPh
2)(PPh
3)
2] ( M = Os, Ru) with zinc powder in the presence of PPh
3 led to the reduction of the carbyne complex to give indenyl-complexes M(η
5C
9H
7(Ph))(PPh
3)
2CI (M = Os, M = Ru). The ruthenium carbyne complexes mer-[RuCI
3(≡CCH=CRR')(PPh
3)
2] were prepared conveniently from a one-pot reaction of RuCI
2(PPh
3)
3 with HC≡CCH(OH)RR' in the presence of HCI (R, R' = Ph, CH
3). Treatment of mer-OsCI
3(≡CCH
2Ph)(PPh
3)
2 with zinc powder and PPh
3 in refluxing THF solution afforded the hydrido-vinylidene complex OsHCI(=C=CHPh)(PPh
3)
3. Reaction of mer-OsCI
3(≡CCH
2Ph)(PPh
3)
2 with H
2O
2 in CH
2CI
2 produced OsCI
3(≡CC(O)Ph)(PPh
3)
2.
Post a Comment