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Oxidative Decarbonylation of an Azacalixpyridine‐Supported Mo(0)‐Tricarbonyl to a Mo(VI)‐Trioxo Complex with Dioxygen in Solution and on Au(111): Determination of Molecular Mechanism

“…The carbonyl complex 1 investigated here also has two MLCT transitions (d→π*(1) and d→π*(2)) [16,17] . These cannot be precisely identified by overlapping with the π→π* of the azacalix ligand (see above).…”

“…Two very intense bands are located at 272 nm and 331 nm. Mo(0) carbonyl complexes are reported to have two MLCT transitions in this region, d→π*(1) and d→π*(2) [16,17] . However, the UV/vis spectrum of the protonated ligand 6 (Scheme S2, Figure S12b and S13b) exhibits two π→π* transitions of the azacalixpyridine ligand in the same wavelength range (π ph →π ph * and π py →π py *, respectively).…”

“…Mo(0) carbonyl complexes are reported to have two MLCT transitions in this region, d!π*(1) and d!π*(2). [16,17] However, the UV/vis spectrum of the protonated ligand 6 (Scheme S2, Figure S12b and S13b) exhibits two π!π* transitions of the azacalixpyridine ligand in the same wavelength range (π ph !π ph * and π py !π py *, respectively). The detected bands thus result from MLCT d!π* and ligand π!π* transitions, whereby the latter are dominant:…”

“…At 454 nm a d-d transition of Mo(0) is observed which disappears upon conversion to the Mo(VI) oxo complex. [16,17] Due to the progressive conversion of the carbonyl complex 1 into the oxo complex 2, the intense π!π* transitions of the ligand shift from 272 nm to 282 nm and from 331 nm to 342 nm. Despite the disappearance of the Mo!CO MLCT transitions, the intensities of the shifted absorption bands hardly change.…”

Reatividade do [Fe(CO)2(eta2-CS2)(PPh 3)2] frente a compostos de Cu(I): síntese de espécies binucleares heterometálicas contendo CS2 em ponte entre Fe(0) e Cu(I)

“…Já o CS 2 constitui um excelente precursor de enxofre para fins de se obter filmes finos de materiais semi-condutores. Assim, considerando o nosso interesse nos carbonilmetais e compostos heteropolimetálicos, este trabalho trata da síntese e caracterização de compostos do tipo [Fe(CO) 3 (µ-CS 2 )(PPh 3 )(CuX)], sendo X = Cl, ClO 4 , dando prosseguimento aos nossos trabalhos envolvendo carbonilmetais [11][12][13].…”