The unsymmetrical diborane(4) derivative [(d(CH 2 P( i Pr) 2 )abB)-Bpin] ( 1 ) proved to be a versatile PBP boryl pincer ligand precursor for Co(I) ( 2a , 4a ), Rh(I) ( 2 - 3b ) and Ir(I/III) ( 2 - 3c , 5 - 6c ) complexes, in particular of the types [(d(CH 2 P( i Pr) 2 )abB)M(PMe 3 ) 2 ] ( 2a - c ) and [(d(CH 2 P( i Pr) 2 )abB)M-PMe 3 ] ( 2b - c ). Whilst similar complexes have been obtained before, for the first time, the coordination chemistry of a homologous series of PBP pincer complexes, in particular the interconversion of the five- and four-coordinate complexes 2a - c / 3a - c , was studied in detail. For Co, instead of the mono phosphine complex 2a , the dinitrogen complex [(d(CH 2 P( i Pr) 2 )abB)Co(N 2 )(PMe 3 )] ( 4a ) is formed spontaneously upon PMe 3 abstraction from 2a in the presence of N 2 . All complexes were comprehensively characterised spectroscopically in solution via multinuclear (VT-)NMR spectroscopy and structurally in the solid state through single-crystal X-ray diffraction. The unique properties of the PBP ligand with respect to its coordination chemical properties are addressed.