Synthese silylierter enamine durch rhodium-katalysierte hydrosilylierung von 1-aza- und 1,4-diaza-1,3-dienen

Brockmann, Monika; Dieck, Heindirk tom

doi:10.1016/0022-328x(86)80352-7

Cited by 9 publications

(1 citation statement)

References 32 publications

Supporting

Mentioning

Contrasting

Order By: Relevance

“…Thus, a new metal-assisted addition reaction to diazadienes may be involved. Other examples for reactions of this type are 1,3-dipolar cycloadditions to M−NC fragments of diazadiene complexes, addition of D 2 to coordinated dad ligands, yielding C −hydrogenated products, andeven catalytic1,4-hydrosilylations of diazadienes …”

Section: Resultsmentioning

confidence: 99%

Reactivity of Platina-β-diketones with 1,4-Diazabuta-1,3-dienes: Synthesis and Characterization of Acylplatinum(II) Complexes with RNCMeCMeNR and RN(H)CHCHN(R)C(O)Me Ligands

et al. 2002

View full text Add to dashboard Cite

The dinuclear platina-β-diketone [Pt2{(COMe)2H}2(μ-Cl)2] (1a) reacts with 2,3-dimethyl-substituted 1,4-diazabuta-1,3-dienes RNCMeCMeNR (R = n-Pr, Ph), yielding the acylplatinum(II) complexes [Pt(COMe)2{(n-Pr)NCMeCMeN(n-Pr)}] (2a) and [Pt(COMe)Cl(PhNCMeCMe=NPh)] (2b), respectively. Constitutions of these complexes were confirmed by 1H and 13C NMR spectroscopy and by single-crystal X-ray diffraction analyses. In these reactions the acyl(hydrido)platinum(IV) complexes [Pt(COMe)2Cl(H)(RNCMeCMeNR)] (3a, R = n-Pr; 3b, R = Ph) were detected (1H NMR spectroscopy) as intermediates, from which complexes 2a,b were formed by reductive elimination of HCl and MeCHO, respectively. Reactions of the platina-β-diketone 1a with diazadiene ligands that are unsubstituted at the 2- and 3-positions, RNCHCHNR (R = n-Pr, i-Pr, c-Hex, t-Bu), afforded platinum(II) complexes of the type [Pt(COMe)Cl{RN(H)CHCHN(R)C(O)Me}] (4a, R = n-Pr; 4b, R = i-Pr; 4c, R = c-Hex; 4d, R = t-Bu). All complexes were characterized by NMR spectroscopy (1H, 13C), and the structure of complex 4d was determined by single-crystal X-ray diffraction as well. The organo ligand is formally obtained by 1,4-addition of MeC(O)−H to the diazadiene ligand RNCHCHNR. On the basis of DFT calculations of the model complex [Pt(COMe)Cl{MeN(H)CHCHN(Me)C(O)Me}] (6) and of the (relaxed) free ligand MeN(H)CHCHN(Me)C(O)Me (7) the electronic structure of complex 6 and the bonding mode of ligand 7 is discussed. DFT calculation of the isomeric acyl(hydrido)platinum(IV) complex [Pt(COMe)2Cl(H)(MeNCHCHNMe)] (9a) indicated that it is 18.2 kcal/mol higher in energy than complex 6. Thus, 9a may be an intermediate in the formation of complex 6.

show abstract

Section: Resultsmentioning

confidence: 99%