A comparative study of the reactivity of isolobal rhenium and molybdenum carbonylmetallates containing a borole, in [Re(η5-C4H4BPh)(CO)3]− (2), a boratanaphthalene, in [Mo(η5-2,4-MeC9H6BMe)(CO)3]− (4a) and [Mo(η5-2,4-MeC9H6BNi-Pr2)(CO)3]− (4b), a boratabenzene, in [Mo(η5-3,5-Me2C5H3BNi-Pr2)(CO)3]− (6) or a dimethylaminocyclopentadienyl ligand, in [Mo(η5-C5H4NMe2)(CO)3]− (7), toward palladium(II), gold(I), mercury(II) and platinum(II) complexes has allowed an evaluation of the role of these π-bonded ligands on the structures and unprecedented coordination modes observed in the resulting metal–metal bonded, heterometallic complexes. The new metallate 6 was reacted with [AuCl(PPh3)], and with 1 or 2 equiv. HgCl2, which afforded the new heterodinuclear complexes [Au{Mo(η5-3,5-Me2C5H3BNi-Pr2)(CO)3}(PPh3)] (Mo–Au) (10) and [Hg{Mo(η5-3,5-Me2C5H3BNi-Pr2)(CO)3}Cl] (Hg–Mo) (11) and the heterometallic chain complex [Hg{Mo(η5-3,5-Me2C5H3BNi-Pr2)(CO)3}2] (Mo–Hg–Mo) (12), respectively. Reactions of the new metallate 7 with HgCl2, trans-[PtCl2(CNt-Bu)2] and trans-[PtCl2(NCPh)2] yielded the heterodinuclear complex [Hg{Mo(η5-C5H4NMe2)(CO)3}Cl] (Mo–Hg) (15), the heterotrinuclear chain complexes trans-[Pt{Mo(η5-C5H4NMe2)(CO)3}2(CNt-Bu)2] (Mo–Pt–Mo) (16) and trans-[Pt{Mo(η5-C5H4NMe2)(CO)3}2(NCPh)2] (Mo–Pt–Mo) (17), the mononuclear complex [Mo(η5-C5H4NMe2)(CO)3Cl] (18), the lozenge-type cluster [Mo2Pt2(η5-C5H4NMe2)2(CO)8] (19) and the heterodinuclear complex [![[upper bond 1 start]](https://www.rsc.org/images/entities/char_e010.gif)
Pt{Mo(η5-C5H4N![[upper bond 1 end]](https://www.rsc.org/images/entities/char_e011.gif)
Me2)(CO)3}(NCPh)Cl](Mo–Pt) (20), respectively. The complexes 11, 16, 17·2THF, 18 and 20 have been structurally characterized by X-ray diffraction and 20 differs from all other compounds in that the dimethylaminocyclopentadienyl ligand forms a bridge between the metals.
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