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Volumn 42, Issue 20, 2003, Pages 6528-6538

Cyclometalated analogues of platinum terpyridine complexes: Kinetic study of the strong σ-donor cis and trans effects of carbon in the presence of a π-acceptor ligand backbone

Author keywords

[No Author keywords available]

Indexed keywords

2,2' BIPYRIDINE DERIVATIVE; BENZENE DERIVATIVE; BROMINE; CARBON; IODINE; LIGAND; METAL; METHANOL; N,N DIMETHYLTHIOUREA; N,N,N',N' TETRAMETHYLTHIOUREA; PLATINUM; PLATINUM COMPLEX; PYRIDINE DERIVATIVE; SOLVENT; THIOUREA DERIVATIVE; UNCLASSIFIED DRUG;

EID: 0141454937     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic034400+     Document Type: Article
Times cited : (126)

References (72)
  • 26
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    • note
    • Note that there is a printing error in ref 19: 1.3-Dibromobenzene must be used as reactant instead of 1,3-dibromopyridine.
  • 27
    • 20244366934 scopus 로고    scopus 로고
    • note
    • 6, which was found to react with the complex to produce the corresponding DMSO compound.
  • 52
    • 20244369051 scopus 로고    scopus 로고
    • note
    • Preliminary calculations have shown that the σ-donor strengths of ammonia and pyridine are very similar.
  • 59
    • 0003577547 scopus 로고
    • Kotowski, M., van Eldik, R., Eds.; Elsevier Science Publisher: New York
    • Inorganic High Pressure Chemistry; Kotowski, M., van Eldik, R., Eds.; Elsevier Science Publisher: New York, 1986; Vol 7, pp 219.
    • (1986) Inorganic High Pressure Chemistry , vol.7 , pp. 219
  • 60
    • 20244372343 scopus 로고    scopus 로고
    • note
    • A referee pointed out that the observed increase in nucleophilic discrimination (0.61 for NCN vs 0.40/0.43)13 could also be due to a decrease in steric discrimination of NCN in comparison with the sterically more hindered reference complexes, and therefore not necessarily due to an electronic effect. If this is the case, a decrease in the ratio of the rate constants in going from unsubstituted to substituted thioureas would be expected since the complex is less sensitive towards steric hindrance on the entering nucleophile. Since such a decrease in comparison with the literature complexes could not be observed, we conclude that the increased nucleophilic discrimination of NCN is mainly due to the electron withdrawing, electrophilicity enhancing π-acceptor effect of the pyridine/phenyl rings.
  • 61
    • 20244376705 scopus 로고    scopus 로고
    • note
    • 2+ has a formal charge of +2 and a calculated NBO charge of +0.83 on the platinum center), we discuss the change in the nucleophilic discrimination in terms of electron density on the platinum center due to electron donation by the better σ-donor phenyl and not in terms of a change in the overall charge on the complex.
  • 72
    • 20244371769 scopus 로고    scopus 로고
    • Manuscript in preparation
    • Jaganyi, D. Manuscript in preparation.
    • Jaganyi, D.1


* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.