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Volumn 48, Issue 17, 2009, Pages 8415-8422

Cationic dimetallic gold hydride complex stabilized by a xantphos-phosphole ligand: Synthesis, X-ray crystal structure, and density functional theory study

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EID: 69549115048     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic901014r     Document Type: Article
Times cited : (60)

References (64)
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    • For a comprehensive review on catalysis by gold complexes or nanoparticles (a)
    • For a comprehensive review on catalysis by gold complexes or nanoparticles see: (a) Hashmi, A. S. K.; Hutchings, G. J. Angew. Chem., Int. Ed. 2006, 45, 7896-7936; and references therein.
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    • For pertinent references in which Au-H bonds are postulated in catalytic cycles, see for example: (b)
    • For pertinent references in which Au-H bonds are postulated in catalytic cycles, see for example: (b) Gonzalez-Arellano, C.; Corma, A.; Iglesias, M.; Sanchez, F. Chem. Commun. 2005, 3451-3453.
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    • note
    • Theoretical calculations carried out at the B3PW91/6-311++G(d, p)//B3PW91 6-31 G(d) level of theory have demonstrated that both conformation of Xantphos-phosphole 1 have nearly the same energy (ΔE = +2.9 kcal/mol) at the same energy. In the first conformation the two phosphorus atom lone pair point towards the plane of symmetry of the ligand (to form, a chelate ligand) whereas in the second conformation (+2.9 kcal/mol) one phosphorus atom lone pair points outside the ligand explaining why a monodentate is formed when [Au-Cl] is reacted. The two conformations are in equilibrium through the inversion of one phosphorus atom of one phosphole ring. DFT calculations indicate that the inversion barrier in this type of 1,2,5-tris aryl substituted phosphole is about 16 kcal/ mol (RB3PW 6-311++G(d,p) level of theory).
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    • note
    • One reviewer of this article suggested that complex 3 could be obtained in pure form by submitting complex 4 to a metathesis with chloride salts. Several attempts were thus made using LiCl as salt in different solvents but each attempt resulted in the formation of 2 and 3 as a mixture.
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    • Despite many attempts, we could not avoid the presence of one very small imaginary frequency at -9.7650 corresponding mainly to the rotation of a phenyl group on one phosphole part of the ligand.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.