This paper presents a new convenient route to prepare osmafuran starting from readily accessible HC≡C CH(OH)C≡CH and OsHCl(CO)(PPh3)3.Treatment of a solution of OsHCl(CO)(PPh3)3 in dichloromethane with HC≡C CH(OH)C...This paper presents a new convenient route to prepare osmafuran starting from readily accessible HC≡C CH(OH)C≡CH and OsHCl(CO)(PPh3)3.Treatment of a solution of OsHCl(CO)(PPh3)3 in dichloromethane with HC≡C CH(OH)C≡CH,followed by the addition of acetic acid,produced osmafuran [Os(CHC(PPh3)CO(CH2CH3))Cl(CO)(PPh3)2]Cl(2).2 has been isolated in good yield and fully characterized.1H and 13C NMR spectra show the characteristic downfield chemical shifts of the ring hydrogen and carbon atoms.NMR and X-ray diffraction data provide strong evidence for the aromatic nature of 2.Probably due to the effect of the phosphonium substituent,2 exhibits remarkable thermal stability,air stability and lower reactivity.展开更多
We studied the reactivity of an osmium vinyl complex containing a coordinated hydroxyl group OsC12（PPh3）2[CH=C（PPh3）- CHPh（OH）] （1） toward bidentate ligand 1,4-bis（diphenylphosphino）butane （DPPB）, acid li...We studied the reactivity of an osmium vinyl complex containing a coordinated hydroxyl group OsC12（PPh3）2[CH=C（PPh3）- CHPh（OH）] （1） toward bidentate ligand 1,4-bis（diphenylphosphino）butane （DPPB）, acid ligand （CO）, base （Cs2CO3） and heat. Two osmium vinyl complexes OsC12（dppb）[CH=C（PPh3）CHPh（OH）] （2） and OsCI2（CO）2（PPh3）[CH=C（PPh3）CHPh（OH）] （3）, as well as two relatively rare phosphonium-containing osmafuran complexes Os（q2-OCOO）（PPha）z[CHC（PPha）CPhO] （4） and OsClz（PPh3）z[CHC（PPh3）CPhO] （5）, were obtained in high yields from these reactions. All products were characterized by NMR spectroscopy, elemental analysis, and their structures were further confirmed by single crystal X-ray diffraction.展开更多
Based on isolobal analogy,the definition of metallafuran was described and its synthetic chemistry was briefly summarized.In the structure of furan,when one of CH groups was replaced by an isolobal metal fragment ML n...Based on isolobal analogy,the definition of metallafuran was described and its synthetic chemistry was briefly summarized.In the structure of furan,when one of CH groups was replaced by an isolobal metal fragment ML n(M=metal;L=ligand),the corresponding organometallic complex was called metallafuran,which should be two possible isomers called a-metallafuran(metal fragment at a-carbon of original furan)and b-metallafuran(metal fragment at b-carbon of original furan).As an organometallic complex,a-metallafuran has two resonant forms:one can be viewed as carbonyl coordinated vinyl metal complex and the other can be viewed as alkoxymetal carbene.Therefore,a-metallafuran was also called chelated vinyl ketone metal complex or oxametallacyclopentadiene in the early literatures.For synthesis of metallafurans,a-metallafurans were very common and easily prepared,for example,from alkynes insertion into acyl metal complexes and so on.While there were rare examples reported for b-metallafurans.In this mini review,the synthetic chemistry of metallafuran was mainly focused on its formation mechanism.展开更多
基金supported by the National Natural Science Foundation of China (20872123, 20801046 and 20925208)Research Fund for the Doctoral Program of Higher Education of China (200803841034)
文摘This paper presents a new convenient route to prepare osmafuran starting from readily accessible HC≡C CH(OH)C≡CH and OsHCl(CO)(PPh3)3.Treatment of a solution of OsHCl(CO)(PPh3)3 in dichloromethane with HC≡C CH(OH)C≡CH,followed by the addition of acetic acid,produced osmafuran [Os(CHC(PPh3)CO(CH2CH3))Cl(CO)(PPh3)2]Cl(2).2 has been isolated in good yield and fully characterized.1H and 13C NMR spectra show the characteristic downfield chemical shifts of the ring hydrogen and carbon atoms.NMR and X-ray diffraction data provide strong evidence for the aromatic nature of 2.Probably due to the effect of the phosphonium substituent,2 exhibits remarkable thermal stability,air stability and lower reactivity.
基金supported by the National Natural Science Foundation of China(21174115 and 21202054)the National Basic Research Program of China (973 Program,2012CB821600)the Program for Changjiang Scholars and Innovative Research Team in University
文摘We studied the reactivity of an osmium vinyl complex containing a coordinated hydroxyl group OsC12（PPh3）2[CH=C（PPh3）- CHPh（OH）] （1） toward bidentate ligand 1,4-bis（diphenylphosphino）butane （DPPB）, acid ligand （CO）, base （Cs2CO3） and heat. Two osmium vinyl complexes OsC12（dppb）[CH=C（PPh3）CHPh（OH）] （2） and OsCI2（CO）2（PPh3）[CH=C（PPh3）CHPh（OH）] （3）, as well as two relatively rare phosphonium-containing osmafuran complexes Os（q2-OCOO）（PPha）z[CHC（PPha）CPhO] （4） and OsClz（PPh3）z[CHC（PPh3）CPhO] （5）, were obtained in high yields from these reactions. All products were characterized by NMR spectroscopy, elemental analysis, and their structures were further confirmed by single crystal X-ray diffraction.
基金supported by the National Natural Science Foundation of China (21302158 and 21472156)the National Basic Research Program of China (2012CB821600)
文摘Based on isolobal analogy,the definition of metallafuran was described and its synthetic chemistry was briefly summarized.In the structure of furan,when one of CH groups was replaced by an isolobal metal fragment ML n(M=metal;L=ligand),the corresponding organometallic complex was called metallafuran,which should be two possible isomers called a-metallafuran(metal fragment at a-carbon of original furan)and b-metallafuran(metal fragment at b-carbon of original furan).As an organometallic complex,a-metallafuran has two resonant forms:one can be viewed as carbonyl coordinated vinyl metal complex and the other can be viewed as alkoxymetal carbene.Therefore,a-metallafuran was also called chelated vinyl ketone metal complex or oxametallacyclopentadiene in the early literatures.For synthesis of metallafurans,a-metallafurans were very common and easily prepared,for example,from alkynes insertion into acyl metal complexes and so on.While there were rare examples reported for b-metallafurans.In this mini review,the synthetic chemistry of metallafuran was mainly focused on its formation mechanism.
