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A novel, versatile and modular route to unsymmetrical diborane(4) derivatives bearing either two different diol moieties or one diol and one diamine moiety is presented. Utilising the very basic approach of reacting a boron nucleophile with a boron electrophile to establish the B–B bond allows a simple variation of the two individual boron moieties. The copper(i) boryl complexes used as nucleophilic boron sources are readily accessible from commercially available symmetrical diborane(4) derivatives, whilst equally readily available boron halide derivatives are used as electrophiles. Seven previously inaccessible diborane(4) derivatives were obtained and fully characterised, including single crystal X-ray structure determinations, illustrating the broad scope of the method. [ABSTRACT FROM AUTHOR]

The unsymmetrical diborane(4) pinB–B((RN)2(C6H4)) (R = Me, Bn) reacts with [(Me3P)4Rh–X] (X = Me, OtBu) giving predominantly either [(Me3P)4Rh–Bpin] or [(Me3P)3Rh–B((RN)2(C6H4))] depending on X. At low temperatures in the presence of excess PMe3 the unprecedented equatorial boryl complex [(Me3P)4Rh–B((MeN)2(C6H4))] is formed. [ABSTRACT FROM AUTHOR]