Producción Científica Profesorado

Pentacoordination at Germanium by Transannular Bonding of Sulfur or Oxygen in an Eight-Membered Ring: An Experimental and Theoretical Study



Andrade López, Noemí

2006

Pentacoordination at Germanium by Transannular Bonding of Sulfur or Oxygen in an Eight-Membered Ring: An Experimental and Theoretical Study. Simplicio González-Montiel 1, Noemí Andrade-López 1, Verónica García-Montalvo 2, Juan Antonio Cogordan 2, José G. Alvarado-Rodríguez 1 . Eur. J. Inorg. Chem. 2006, 4752-4760. ISSN (on line) 1099-0682. DOI: 10.1002/ejic.200600424


Abstract


Treatment of LnGeCl4n with D(C6H4SH)2 in the presence of nBuLi leads to the formation of the stable compounds D(C6H4S)2GeL1L2 (for D = S, L1 = Cl, L2 = Ph, 1 and L1 = L2 = Ph, 3; for D = O, L1 = Cl, L2 = Et, 4 and L1 = L2 = Ph, 5). The S(C6H4S)2Ge(Ph)Br compound (2) has been synthesised by halogen exchange from 1 and potassium bromide. X-ray structure determinations of complexes 15 reveal that the germanium atom acts as an acceptor atom displaying an intramolecular transannular interaction with the chalcogen D atom. The geometry of the pentacoordinate Ge atom in the title compounds is described as distorted trigonal bipyramidal with a 6431?% distortion displacement. The D?Ge (D = S, O) hypercoordinate interaction was studied by DFT methods using correlation consistent basis sets and relativistic ECP for Ge. NBO analysis showed that this interaction can be explained in terms of the interplay of covalent and Coulombic interactions.



Producto de Investigación




Artículos relacionados

Study of the D?Sb (D = O, S) Transannular Interaction in Sb-Monohalogenated Dibenzostibocines ? An E...

Pentacoordination at Germanium by Transannular Bonding of Sulfur or Oxygen in an Eight-Membered Ring...

Hypervalence at tin(IV) by transannular bonding of sulfur in an eight-membered ring: The case of dib...

Synthesis and crystal structures of cis-palladium(II) and cis-platinum(II) complexes containing dipy...

Structural differences in eight- and ten-membered heterocyclic tin compounds displaying transannular...

Boron heterocycles derived from 2-guanidinobenzimidazole

cis-Palladium(II) complexes of derivatives of di-(2-pyridyl)methane: Study of the influence of the b...

Synthesis, Characterisation and Properties of As-Monohalogenated Dibenzoarsocines S(C6H4S)2AsHal (Ha...

Boron and transition metal compounds derived from 2-uroylbenzimidazole

Synthesis, Characterisation and Properties of As-Monohalogenated Dibenzoarsocines S(C6H4S)2AsHal (Ha...