Синтез и строение новых дигалогендицианоауратных комплексов

Abstract

Interaction of tetraorganylphosphonium halides with potassium dichloro-, dibromo- and diiododicyanoaurate in water followed by recrystallization from acetonitrile has been used to synthesize gold(III) ionic complexes [Me 4 P][Au(CN) 2 Cl 2 ] ( 1 ), [Ph 3 PR][Au(CN) 2 Hal 2 ] (Hal = Cl, R = (CH 2 ) 6 Me ( 2 ), (CH 2 ) 2 C(O)OH ( 3 ); Hal = Br, R = CH 2 CN ( 4 ); Hal = I, R = CH 2 CN ( 5 )) and [Ph 3 PCH=CHPPh 3 ][Au(CN) 2 Cl 2 ] 2 ( 6 ). In a similar way complex [Ph 4 Sb][Au(CN) 2 Cl 2 ] ( 7 ) has been obtained by the interaction of tetraphenylantimony chloride with potassium dichlorodicyanoaurate. Complexes 3 , 5 – 7 have been structurally characterized by the X-ray analysis method. According to the X-ray data phosphorus and antimony atoms in crystals 3 , 5 – 7 have a slightly distorted tetrahedral coordination (the CPC bond angles are 107.5(2)-111.8(3)° ( 3 ), 106.0(3)-111.5(3)° ( 5 ), 106.7(4)-111.8(4)° ( 6 ), the CSbC bond angles are 100.5(7)-114.6(5)° ( 7 ); the P–C bond lengths are 1.788(5)-1.807(5) Å ( 3 ), 1.765(6)-1.821(6) Å ( 5 ), 1.781(8)-1.810(8) Å ( 6 ); the Sb–C bond lengths are 2.070(11)-2.121(12) Å ( 7 )). Gold atoms in [Au(CN) 2 Hal 2 ] - anions have a slightly distorted square planar coordination (the HalAuHal and CAuC trans -angles are quite close to 180°; the CAuHal cis -angles vary from 88.05° to 92.48°), the Au–Hal bond lengths are 2.328(3) Å ( 3 ), 2.393(2), 2.411(2) Å ( 6 ), 2.4223(12) Å ( 7 ) for Au–Cl and 2.609(3), 2.598(3) Å ( 5 ) for Au–I; the Au–C bond lengths are 1.981(7) Å ( 3 ), 1.996(7), 2.006(8) Å ( 5 ), 1.978(12), 2.001(13) Å ( 6 ), 2.040(15) ( 7 ). In crystal 5 two types of crystallographically independent centrosymmetric [Au(CN) 2 I 2 ] - anions are observed. The structural organization of complexes 3 , 5 – 7 is caused by the different noncovalent interactions: С–H∙∙∙N≡C 2.55–2.74 Å ( 3 , 5 – 7 ), O–H∙∙∙N≡C 2.03 Å, С–H∙∙∙O=C 2.52 Å, C–H∙∙∙Cl–Au 2.88–2.93 Å ( 3 ), Au–I∙∙∙I–Au 3.925(4) Å ( 5 ), C–H∙∙∙Cl–Au 2.91 Å ( 6 ).