Heteroallenes coordinated

Heptane-4,6-dione, decafluoro-metal complexes decomposition, 385 Heptane-2,4,6-trione metal complexes, 399 Heteroallenes coordinated reactivity, 579 metal complexes, 579 Heterocyclic nitrogen compounds basic pKa... 

Novel coordination compounds formed from CS2 and heteroallenes. H. Werner, Coord. Chem. Rev., 1982, 43,165-185 (53). 

Coordinated CS2 groups can react via dimerization and abstraction of CS2, as can be seen in a survey of reactions of a rhodium(I) phosphine complex with CS2 (Scheme 1). The dimerization can be throught to proceed through a nucleophilic attack on the carbon atom of CS2 via an end-on intermediate of the heteroallene fragment.1011... 

Similar reactions can be performed starting from varions heteroallenes (CO2, CS2, RN=C=NR, RN=C=S, RN=C=0) giving stable monomeric five-coordinated anionic complexes. Addition of diazoalkane to phosphanozir-conocenes leads to stable N-metalphosphazines (equation 19). 

Analogous heterobimetallic tripodal amido complexes 1275 (M = Fe, Ru) undergo highly selective reactions with heteroallenes X=C=Y (C02, CS2, OGNPh, SCNMe, SCNPh) to yield the insertion products 1276 (Equation (65)).962 Single crystal X-ray structures of the products (1276 M = Fe X = Y = S X = S, Y = NPh) established the mode of coordination of the substrates to the two metal centers as depicted in Equation (65). The Zr-Fe complex CpFe(CO)2Zr(OBut)Cp2 reacts with 1 equiv. of CS2 to form the analogous stable dithiocarboxylate complex.963... 

On substitution of the two CRj groups in the allene molecule by isoelectronic hetero groups or atoms X and Y (X, Y = O, S, NR), molecules X=C=Y are formed, which are called pseudo- or hetero-allenes. This chapter deals with the heteroallenes CSj and COS and the ligands based on these two molecules, the heteroallyls. The heteroallenes themselves have been reviewed by Gattow and Behrendt and Reid respectively. Their coordinating properties have been compared recently by Ibers. Assuming X to be preferred over Y for coordination, both end-on coordination by X and side-on ( / ) coordination by the C=X double bond occurs, whereas for X=Y=S bridging coordination between two metals is also found. 

The C-H insertion reaction of phosphanylidene carbenoid is also found as a typical carbenoid reaction. The copper-mediated oxidative coupling reactions are powerful synthetic tools to construct some conjugated systems with the P=C skeleton, which are operated by treatment of oxygen. Lithium phosphanylidene carbenoids are applicable to synthesize the heavier heteroallenic compounds and stable biradical compounds. Moreover, an intriguing trimerization of phosphanylidene carbenoids is used to give the triphosphafulvene as an isomer of triphosphabenzene, which will lead to a novel organic chemistry. Indeed, the mentioned low-coordinated phosphorus compounds may well be applied to the synthesis of novel materials [5,64,65]. 

The preparation and properties of phosphanylidene carbenoids, a class of inherently unstable low coordinated phosphorus compounds are then described by M. Yoshifuji and S. Ito. The kinetic stabilization method reported by the authors, allows them to develop a rich chemistry leading to phosphaethenes, phosphaalkynes, heavier heteroallenic compounds, stable biradical derivatives etc... 

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