Mono‐ and Diprotonation of the Superbasic Bisguanidine 1,2‐Bis(N,N,N′,N′‐tetramethylguanidino)benzene (btmgb) and PtII and PtIV Complexes of Chelating Bisguanidines and Guanidinates

Abstract

New Pt complexes of chelating bisguanidines and guanidinate ligands were synthesized and characterized. 1,2-Bis(N,N,N',N'-tetramethylguanidino)benzene (btmgb) was used as a neutral chelating bisguanidine ligand, and 1,3,4,6,7,8-hexahydro-2H-pyrimido[1,2-a]pyrimidinate (hpp(-)) as a guanidinate ligand. The salts [btmgbH]+[HOB(C6F5)3](-) and [btmgbH2]Cl2 and the complexes [(btmgb)PtCl2], [(btmgb)PtCl(dmso)]+[PtCl3(dmso)](-), and [(btmgb)PtCl(dmso)]+[Cl(-)] were synthesized and characterized. In the [btmgbH]+ cation the proton is bound to only one N atom. In the other complexes, both imine N atoms are coordinated to the Pt II, thus adopting a eta2-coordinational mode. The hpp(-) anion, which usually prefers a bridging binding mode in dinuclear complexes, is eta2-coordinated in the Pt IV complex [(eta2-hpp)(hppH)PtCl2(N(H)C(O)CH3)], which is formed (in low yield) by reaction between cis-[(hppH)2PtCl2] and H2O2 in CH3CN.