The synthesis and X-ray analysis of complexes [(micro-1,12-C2B10H10){Au(PPh3)}2] and [(micro-1,2-C2B10H10){Au(PMe3)}2] have provided the experimental data needed to analyse two points. The first point is the use of these data to carry out a computational study with the aim of comparing the electronic structures and relative stabilities of the organometallic isomers [(micro-1,n-C2B10H10){Au(PR3)}2] (n=2, 7, 12; R=Ph, Me) with those of the parent carborane clusters ortho-, meta- and para-carborane and the influence of the monophosphine substituents. The second point is focused in the influence of the steric demand of the monophosphine in the presence or not of aurophilic interactions in the ortho derivatives [(micro-1,2-C2B10H10){Au(PR3)}2] (R=Me, Ph). The photoluminescent behaviour of both the carboranes and the organometallic complexes is presented.
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