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Structures and bonding character of Ge center dot center dot center dot CO weakly bonding complexes
Bu, YX; Cao, ZH
刊名JOURNAL OF PHYSICAL CHEMISTRY B
2002-02-21
DOI10.1021/jp014095i
106期:7页:1613-1621
收录类别SCI
文章类型Article
WOS标题词Science & Technology ; Physical Sciences
类目[WOS]Chemistry, Physical
研究领域[WOS]Chemistry
关键词[WOS]ELECTRON CORRELATION LEVELS ; DENSITY-FUNCTIONAL THEORY ; HEME-PROTEINS ; CORRELATION-ENERGY ; RESONANCE RAMAN ; BINDING ; MYOGLOBIN ; SYSTEMS ; GAS
英文摘要The structural properties and the bonding character of the subcarbonyl Ge, GeCO, and Ge(CO)(2) in their singlet and triplet states have been investigated using B3LYP, B3P86, B3PW91, and MP2 methods at 6-311+G* basis set level. Results indicate that GeCO species possesses a (3)Sigma ground state with a singlet (1)Sigma excited state above by 17 kcal/mol at CCSD(T)/6-311+G* level. The ground-state GeCO may be classified as carbene-like, and its COdelta- moiety possesses CO- character. Formation of GeCO causes the weakening of CO bonding; the produced Ge-C bond is weakly bonding consisting of a weak sigma-bond and two weak pi-bonds. The calculated dissociation energy is 16.8 kcal/mol at CCSD(T)/6-311+G* level. The corresponding potential well for the bending mode is shallow; therefore, GeCO molecule is easily bent. For Ge(CO)(2), there exist two v-type structures for singlet state and one for triplet state; no linear ones are found for either state. The singlet state (1 (1)A(1)) is more stable by 24.1 kcal/mol than the 2 (1)A(1) state and by 36.6 kcal/mol than the B-3(1) state at CCSD(T)/6-311+G* level; thus it may be considered as the ground state. The bond lengths in the 1 (1)A(1) ground state are very close to those in GeCO species, but the angleGeCO angle is bent by similar to10degrees and the angleCGeC angle is only similar to76degrees. The Ge-C bond lengths in the 2 (1)A(1) state are longer by 0.03-0.07 Angstrom than those of the 1 (1)A(1) state, and the angleGeCO and angleCGeC angles are 140-144degrees and 119-125degrees, being significantly different from those of the ground state. The corresponding triplet state has similar to50degrees of angleCGeC angle and 162-166degrees of angleGeCO angle, but its Ge-C and C-O bonds are longer than those in the 1 (1)A(1) state by similar to0.07 and 0.03 Angstrom, respectively. These Ge(CO)(2) species have essentially carbene-like character and should be referred to as bicarbonyl carbene-like. Comparison of the CO-dissociating energies between GeCO and Ge(CO)(2) in their ground states indicates that the first-CO-dissociating energy of Ge(CO)(2) is smaller by similar to8.7 kcal/mol than that of GeCO; the averaged one over two COs is also smaller than that of GeCO. Detailed bonding analysis has implied that the possibility is small for the existence of the polycarbonyl Ge with more than two COs. This prediction may be also true for similar carbonyl complexes containing other nonmetal and nontransition metal atoms or clusters. Further study is very necessary.
语种英语
WOS记录号WOS:000173981900017
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被引频次:7[WOS]   [WOS记录]     [WOS相关记录]
文献类型期刊论文
条目标识符http://cas-ir.dicp.ac.cn/handle/321008/139063
专题中国科学院大连化学物理研究所
作者单位1.Shandong Univ, Inst Theoret Chem, Jinan 250100, Peoples R China
2.Dalian Inst Chem Phys, State Key Lab Mol React Dynam, Dalian 116023, Peoples R China
3.Heze Med Coll, Chem Grp, Heze 274030, Peoples R China
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Bu, YX,Cao, ZH. Structures and bonding character of Ge center dot center dot center dot CO weakly bonding complexes[J]. JOURNAL OF PHYSICAL CHEMISTRY B,2002,106(7):1613-1621.
APA Bu, YX,&Cao, ZH.(2002).Structures and bonding character of Ge center dot center dot center dot CO weakly bonding complexes.JOURNAL OF PHYSICAL CHEMISTRY B,106(7),1613-1621.
MLA Bu, YX,et al."Structures and bonding character of Ge center dot center dot center dot CO weakly bonding complexes".JOURNAL OF PHYSICAL CHEMISTRY B 106.7(2002):1613-1621.
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