The effect of coordination of alkanes, Xe and CO2 (η1-OCO) on changes in spin state and reactivity in organometallic chemistry: a combined experimental and theoretical study of the photochemistry of CpMn(CO)3

A series of diastereoisomeric square planar nickel(II) diperchlorate complexes, [Ni(L)](ClO4)2{L= isomeric Me8[14]ane (LAα, LBα or LCα)}undergo axial ligand addition reactions with NO3-, Cl-, Br-, SCN- or ClO4- to yield six coordinate octahedral derivatives [NiL(X)x(Y)y].z(H2O)(X=NO3,Cl, Br or SCN; Y= ClO4; x = 1 or 2; y = 1 or 0 and z = 0, 1 or 2). The products have been characterized on the basis of analytical, spectroscopic, magnetic and conductance data. All the derivatives are unstable in open air except one derivative and revert back to original square planar complexes. Antifungal activities of the ligands and their nickel(II) complexes have been investigated against some phytopathogenic fungi. The Chittagong Univ. J. Sci. 40(1) : 122-147, 2019

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Comparative theoretical study on the addition reactions of MeOH to silabenzenes and germabenzenes

Computational and Theoretical Chemistry ◽

10.1016/j.comptc.2016.01.001 ◽

2016 ◽

Vol 1078 ◽

pp. 88-95

Author(s):

Yan Wang ◽

Xiaolan Zeng

Keyword(s):

Theoretical Study ◽

Addition Reactions

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First Examples of Homogeneous Catalytic Cyclotrimerization and Polymerization of Phenylacetylene and Copolymerization of Phenylacetylene and Norbonene with Dinuclear Complexes Containing Unbridged Metal-Metal Quadruple Bond

Collection of Czechoslovak Chemical Communications ◽

10.1135/cccc20031094 ◽

2003 ◽

Vol 68 (6) ◽

pp. 1094-1104 ◽

Cited By ~ 5

Author(s):

Konstantinos Mertis ◽

Stavros Arbilias ◽

Demos Argyris ◽

Nikos Psaroudakis ◽

Jiří Vohlídal ◽

...

Keyword(s):

Dinuclear Complexes ◽

Addition Reactions ◽

Polymer Yield ◽

Quadruple Bond ◽

Metal Metal ◽

Medium Activity ◽

Copolymer Structure ◽

Almost All ◽

Ligand Addition ◽

Low Activity

First examples of application of dinuclear complexes containing unbrigded metal-metal quadruple bond as catalysts in cyclotrimerization, oligomerization and polymerization of substituted acetylene are reported. The d4-d4 dinuclear complexes (Bu4N)2[Re2X8] (1) (1a, X = Cl; 1b, X = Br and 1c, X = I) show low activity and the complex [Mo2Cl4(MeOH)2(PPh3)2] (2) medium activity in cyclotrimerization and oligomerization of phenylacetylene (PA). In contrast, the tungsten-based d4-d4, complex Na4[W2Cl8] (3) exhibits high polymerization activity (polymer yield above 90%) and ca 75% cis-selectivity in tetrahydrofuran. The activity and cis-stereoselectivity of these single-component catalysts decrease in the order 3 >> 2 >> 1, which is proportional to the metal-metal quadruple bond propensity towards ligand addition reactions. Complex 3 induces metathesis polymerization of norbornene (NBE) to poly(cyclopentene-1,3-diylvinylene) with 82% cis-selectivity and copolymerization of PA and NBE to almost all-cis high-molecular-weight copolymer containing cyclopentene-1,3-diylvinylene units, which is free of longer sequences of both PA and NBE units. This suggests that also homopolymerization of PA with 3 proceeds by the metathesis mechanism and that the PA/NBE copolymer structure is close to the alternating one.

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