Reactions des organomagnesiens sur les dichlorostannyl et -germyl porphyrines: etude du mecanisme primaire

trans-Difluorosilicon(IV) Complexes of Tetra-p-tolylporphyrin and Tetrakis(p-(trifluoromethyl)phenyl)porphyrin: Crystal Structures and Unprecedented Reactivity in Hexacoordinate Difluorosilanes1

“…Porphyrins − and phthalocyanines 23,26 are macrocyclic ligands which provide a restricted geometry where the non-nitrogen ligands are in a trans configuration. Although there are numerous examples of germanium(IV) − and tin(IV) ,,,− porphyrin complexes, there were only four reports of silicon(IV) 31,58-60 porphyrin complexes prior to our work. We recently reported a high-yield route toward the synthesis of the novel (porphyrinato)silicon(IV) complexes (TTP)SiX 2 (TTP = the dianion of tetra- p -tolylporphyrin; X = Cl, F, O 3 SCF 3 ) and the first X-ray structure of a silicon porphyrin that confirmed the trans geometry of the triflate groups …”

Stereochemical Control in Metalloporphyrin Chemistry: Synthesis and Characterization of cis- and trans-Sn(porphyrin)Ph2

“…In spite of the fact that the covalent radius of Sn is rather large, being roughly in between that of Ti and Zr, all reported derivatives of general formula Sn(por)L 2 (L = e.g. F, Cl, OMe, OH) show trans geometries. , Tin porphyrin dialkyls were first reported by Pommier − but could not be isolated because of their photoactivity and O 2 sensitivity. Kadish recently prepared the first porphyrin complexes containing a stable tin−carbon bond by oxidative addition of MeI to Sn(II)(Por) .…”

Some aspects of organometallic chemistry in metalloporphyrin chemistry: synthesis, chemical reactivity, and electrochemical behavior of porphyrins with metal-carbon bonds

“…TPP)Ge(R)2, where R = CH3, rc-C3H7, n-C8H17, and C6H5, were first synthesized from (TPP)GeCl2 as NMR shift reagents.220,221 Later, other (TPP)M(R)2 complexes were synthesized by treating (TPP)MC12 with RMgX, where M = Ge and R = C2H5, n-C3H7, n-C4H9, i-C4H9, CH2Si(CH3)3, CH2CH=CH2, or n-C6Hi3 or where M = Sn and R = C2H5 or CH^UCH^ 224,225,227. Most of these complexes have only been characterized in solution.…”