Neutral nickel sigma -acetylide complex [Ni(C=CPh)(2)(PBu3)(2)] is a novel initiator for the polymerization of styrene in CHCl3 over a range of polymerization temperature from 40 degreesC to 60 degreesC. The polystyre...Neutral nickel sigma -acetylide complex [Ni(C=CPh)(2)(PBu3)(2)] is a novel initiator for the polymerization of styrene in CHCl3 over a range of polymerization temperature from 40 degreesC to 60 degreesC. The polystyrene obtained was a syndio-rich atactic polymer and its weight-average molecular weight reached 279000. The mechanism of the polymerization was discussed and a radical mechanism was proposed.展开更多
The platinum(II) terpyridyl acetylide complex [Pt(terpy)(C≡CR)]ClO4 (terpy=2,2'∶6'2''-terpyridine, R=CH2CH2CH3) (1) was incorporated into Nafion membranes. At high loading the dry membranes exhibit i...The platinum(II) terpyridyl acetylide complex [Pt(terpy)(C≡CR)]ClO4 (terpy=2,2'∶6'2''-terpyridine, R=CH2CH2CH3) (1) was incorporated into Nafion membranes. At high loading the dry membranes exhibit intense photoluminescence with max at 707 nm from the 3MMLCT state, which was not observed in fluid solution. Upon exposure to the vapor of polar volatile organic compounds (VOC), this photoluminescence was significantly red-shifed. This process was fully reversible when the VOC-incorporated membrane was dried in air. The dramatic and reversible changes in the emission spectra made the Nafion-supported complex as an interesting sensor candi-date for polar VOC.展开更多
A tetranuclear Li2Cr2 acetylide precursor complex, [Li(Tp)crm(c=CSiMe3)2(/,t3-pz)]2· (n-pentane)2 (Tp = hydridotris(pyra- zolyl)borate, pz = pyrazolate) (1) has been synthesized and characterized. The X-ray struc...A tetranuclear Li2Cr2 acetylide precursor complex, [Li(Tp)crm(c=CSiMe3)2(/,t3-pz)]2· (n-pentane)2 (Tp = hydridotris(pyra- zolyl)borate, pz = pyrazolate) (1) has been synthesized and characterized. The X-ray structure analysis shows that the complex contains a Li2Cr2 core bridged by two ,u3-pyrazolates. The magnetic data exhibit the existence of weak antiferromagnetic in- teraction in the cluster.展开更多
The catalytic activities of nine neutral nickel and palladium a-acetylide complexes [M=(C=CR)2(PR'3)2)M=Ni,Pd; R=Ph,CH2OH,CH2OOCH3,CH2OOCPh,CH2OOCPhOH-o; R'=Ph,Bu] are compared.Among them,Ni(Cs=CPh)2-(PBuj)2 s...The catalytic activities of nine neutral nickel and palladium a-acetylide complexes [M=(C=CR)2(PR'3)2)M=Ni,Pd; R=Ph,CH2OH,CH2OOCH3,CH2OOCPh,CH2OOCPhOH-o; R'=Ph,Bu] are compared.Among them,Ni(Cs=CPh)2-(PBuj)2 shows the highest catalytic activity and gives the polystyrene with high molecular weight(Mw=188800)and a syndio-rich microstructure.The catalytic behavior of transition metal acetylides is related to metal,phosphine,and alkynyl ligands bonded to the metal atoms.展开更多
A series of polypyridine ruthenium （II） acetylide complexes, [（tpy）（bpy）RuC≡CC6H4R]^＋ （tpy = 2,2＇：6＇,2＂-terpyridine, bpy = 2,2＇-bipyridine; R = F （1）, C1 （2）, H （3）, Me （4） and OMe （5）） are in...A series of polypyridine ruthenium （II） acetylide complexes, [（tpy）（bpy）RuC≡CC6H4R]^＋ （tpy = 2,2＇：6＇,2＂-terpyridine, bpy = 2,2＇-bipyridine; R = F （1）, C1 （2）, H （3）, Me （4） and OMe （5）） are investigated theoretically to explore their electronic structures and spectroscopic properties. Their ground/excited state geometries, electronic structures and spectroscopic properties are first calculated using density functional theory （DFT） and time-dependent DFT （TDDFT）. The absorption and emission spectra of the complexes in acetonitrile solution are also obtained by using TDDFT （B3LYP） method associated with the CPCM model. The calculations show that the energy levels of HOMOs for 1-5 are sensitive to the substituent on phenylacetylide ligand and increase with the same order of the electron-donating ability of the substituents; however, those of polypyridine-based LUMOs vary slightly. The lowest-energy absorptions and emissions for 1-5 are progressively red-shifted in the order of 1 ~ 2 〈 3 〈 4 〈 5 when the electron-donating groups are introduced into the phenylacetylide [igand. The phosphorescence of 1 are attributed to {[dxz（Ru） ＋π（C≡C）]→[π^＊（tpy）]} （3MLCT/3LLCT） transition, whereas those of 2-5 are originated from { [dxz/dxy（Ru）＋ π（C ≡C）＋g（C6H4R）] → [＊（tpy/bpy）] } （3MLCT/3LLCT） transitions.展开更多
文摘Neutral nickel sigma -acetylide complex [Ni(C=CPh)(2)(PBu3)(2)] is a novel initiator for the polymerization of styrene in CHCl3 over a range of polymerization temperature from 40 degreesC to 60 degreesC. The polystyrene obtained was a syndio-rich atactic polymer and its weight-average molecular weight reached 279000. The mechanism of the polymerization was discussed and a radical mechanism was proposed.
基金Project supported by the Ministry of Science and Technology of China (Nos. G2000078104 G2000077502) and the National Natural Science Foun-dation of China and Bureau for the Basic Research of Chinese Academy of Sciences.
文摘The platinum(II) terpyridyl acetylide complex [Pt(terpy)(C≡CR)]ClO4 (terpy=2,2'∶6'2''-terpyridine, R=CH2CH2CH3) (1) was incorporated into Nafion membranes. At high loading the dry membranes exhibit intense photoluminescence with max at 707 nm from the 3MMLCT state, which was not observed in fluid solution. Upon exposure to the vapor of polar volatile organic compounds (VOC), this photoluminescence was significantly red-shifed. This process was fully reversible when the VOC-incorporated membrane was dried in air. The dramatic and reversible changes in the emission spectra made the Nafion-supported complex as an interesting sensor candi-date for polar VOC.
基金financially supported by the National Natural Science Foundation of China (20801022, 21172084)the Program for New Century Excellent Talents in University of China (NCET-10-0406)+1 种基金the Program for Changjiang Scholars and Innovative Research Team in University (IRT0953)Self-Determined Research Funds of CCNU from the Col- leges' Basic Research and Operation of MOE (CCNU09A02002, CCNU11C01002)
文摘A tetranuclear Li2Cr2 acetylide precursor complex, [Li(Tp)crm(c=CSiMe3)2(/,t3-pz)]2· (n-pentane)2 (Tp = hydridotris(pyra- zolyl)borate, pz = pyrazolate) (1) has been synthesized and characterized. The X-ray structure analysis shows that the complex contains a Li2Cr2 core bridged by two ,u3-pyrazolates. The magnetic data exhibit the existence of weak antiferromagnetic in- teraction in the cluster.
文摘The catalytic activities of nine neutral nickel and palladium a-acetylide complexes [M=(C=CR)2(PR'3)2)M=Ni,Pd; R=Ph,CH2OH,CH2OOCH3,CH2OOCPh,CH2OOCPhOH-o; R'=Ph,Bu] are compared.Among them,Ni(Cs=CPh)2-(PBuj)2 shows the highest catalytic activity and gives the polystyrene with high molecular weight(Mw=188800)and a syndio-rich microstructure.The catalytic behavior of transition metal acetylides is related to metal,phosphine,and alkynyl ligands bonded to the metal atoms.
基金supported by the National Natural Science Foundation of China(Grant No.51073048)the National Natural Science Foundation ofHei Long Jiang Province of China(Grant No.B201102)+1 种基金the Science Foundation for Leaders in Academe of Harbin City of China(Grant No.2013RFXXJ024)the Science Foundation for Elitists of Harbin University of Science and Technology
文摘A series of polypyridine ruthenium （II） acetylide complexes, [（tpy）（bpy）RuC≡CC6H4R]^＋ （tpy = 2,2＇：6＇,2＂-terpyridine, bpy = 2,2＇-bipyridine; R = F （1）, C1 （2）, H （3）, Me （4） and OMe （5）） are investigated theoretically to explore their electronic structures and spectroscopic properties. Their ground/excited state geometries, electronic structures and spectroscopic properties are first calculated using density functional theory （DFT） and time-dependent DFT （TDDFT）. The absorption and emission spectra of the complexes in acetonitrile solution are also obtained by using TDDFT （B3LYP） method associated with the CPCM model. The calculations show that the energy levels of HOMOs for 1-5 are sensitive to the substituent on phenylacetylide ligand and increase with the same order of the electron-donating ability of the substituents; however, those of polypyridine-based LUMOs vary slightly. The lowest-energy absorptions and emissions for 1-5 are progressively red-shifted in the order of 1 ~ 2 〈 3 〈 4 〈 5 when the electron-donating groups are introduced into the phenylacetylide [igand. The phosphorescence of 1 are attributed to {[dxz（Ru） ＋π（C≡C）]→[π^＊（tpy）]} （3MLCT/3LLCT） transition, whereas those of 2-5 are originated from { [dxz/dxy（Ru）＋ π（C ≡C）＋g（C6H4R）] → [＊（tpy/bpy）] } （3MLCT/3LLCT） transitions.
