The surprising transformation of the saturated diamine (iPr)NHCH(2)CH(2)NH(iPr) to the unsaturated diazaethene [(iPr)NCH═CHN(iPr)](2-) via the synergic mixture nBuM, (tBu)(2)Zn and TMEDA (where M = Li, Na; TMEDA = N,N,N',N'-tetramethylethylenediamine) has been investigated by multinuclear NMR spectroscopic studies and DFT calculations. Several pertinent intermediary and related compounds (TMEDA...

A series of novel Pd(ii) complexes with chelating mono(imidazolin-2-imine) and bis(imidazolin-2-imine) ligands were synthesized. The crystal structures of [Pd(DMEAIm(iPr))Cl2] and [Pd(DPENIm(iPr))Cl2] were determined by X-ray diffraction analysis. The reactivity of the six Pd(ii) complexes, namely, [Pd(en)Cl2], [Pd(EAIm(iPr))Cl2], [Pd(DMEAIm(iPr))Cl2], [Pd(DPENIm(iPr))Cl2], [Pd(BL(iPr))Cl2] and...

ABSTRACT Several new monophosphorylated 2,6-diaminopyridine ligands bearing PiPr2 and PtBu2 units (PNNH2-iPr, PNNH2-tBu, PNNHMe-iPr, and PNNHEt-iPr) are prepared by treatment of the respective 2,6-diaminopyridines with the chlorophosphines PiPr2Cl and PtBu2Cl in the presence of a base. Treatment of anhydrous FeCl2 with 1 equiv of these afforded the tetracoordinated coordinatively unsaturated 14...

The bis-carbonyl Fe(II) complex trans-[Fe(PNP-iPr)(CO)2Cl]+ reacts with Zn as reducing agent under a dihydrogen atmosphere to give the Fe(II) hydride complex cis-[Fe(PNP-iPr)(CO)2H]+ in 97% isolated yield. A crucial step in this reaction seems to be the reduction of the acidic NH protons of the PNP-iPr ligand to afford H2 and the coordinatively unsaturated intermediate [Fe(PNPH-iPr)(CO)2]+ bear...

The synthesis of the first Cu2(m-S) complex, {(IPr*)Cu}2(m-S) (IPr* 1⁄4 1,3-bis(2,6-(diphenylmethyl)-4methylphenyl)imidazol-2-ylidene; 1), has been accomplished via three synthetic routes: (1) salt metathesis between (IPr*)CuCl and Na2S; (2) silyl-deprotection reaction between (IPr*)Cu(SSiMe3) and (IPr*)CuF; and (3) acid–base reaction between (IPr*)Cu(SH) and (IPr*)Cu(OBu). The X-ray crystal st...