Organometallic building blocks with amino-substituted cyclopentadienyl and boratabenzene ligands for the synthesis of heterometallic complexes and clusters

Abstract

A comparative study of the reactivity of isolobal rhenium and molybdenum carbonylmetallates containing a borole, in [Re(eta5-C4H4BPh)(CO)3]- (2), a boratanaphthalene, in [Mo(eta5-2,4-MeC9H6BMe)(CO)3]- (4a) and [Mo(eta5-2,4-MeC9H6BNi-Pr2)(CO)3]- (4b), a boratabenzene, in [Mo(eta5-3,5-Me2C5H3BNi-Pr2)(CO)3]- (6) or a dimethylaminocyclopentadienyl ligand, in [Mo(eta5-C5H4NMe2)(CO)3]- (7), toward palladium(II), gold(I), mercury(II) and platinum(II) complexes has allowed an evaluation of the role of these pi-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(eta5-3,5-Me2C5H3BNi-Pr2)(CO)3}(PPh3)] (Mo-Au) (10) and [Hg{Mo(eta5-3,5-Me2C5H3BNi-Pr2)(CO)3}Cl] (Hg-Mo) (11) and the heterometallic chain complex [Hg{Mo(eta5-3,5-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(eta5-C5H4NMe2)(CO)3}Cl] (Mo-Hg) (15), the heterotrinuclear chain complexes trans-[Pt{Mo(eta5-C5H4NMe2)(CO)3}2(CNt-Bu)2] (Mo-Pt-Mo) (16) and trans-[Pt{Mo(eta5-C5H4NMe2)(CO)3}2(NCPh)2] (Mo-Pt-Mo) (17), the mononuclear complex [Mo(eta5-C5H4NMe2)(CO)3Cl] (18), the lozenge-type cluster [Mo2Pt2(eta5-C5H4NMe2)2(CO)8] (19) and the heterodinuclear complex [[upper bond 1 start]Pt{Mo(eta5-C5H4N[upper bond 1 end]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.

Hexa- and Octanuclear Heterometallic Clusters with Copper–, Silver–, or Gold–Molybdenum Bonds and d10–d10 Interactions

“…Thus, replacing the Cp ligand with a functionalized Cp may be sufficient, for both steric and electronic reasons, to bring about significant structural changes in the corresponding clusters. Further reasons for our interest in a comparative reactivity study between [MoCp­(CO) 3 ] − and the amino-substituted derivative [Mo­(η 5 -C 5 H 4 NMe 2 )­(CO) 3 ] − ( 5 ) toward the d 10 complexes [Cu­(NCMe) 4 ]­BF 4 , AgBF 4 and [N­( n -Bu) 4 ]­[AuBr 2 ], are based on previous results which are briefly recalled below.…”

“…Indeed, a series of isolobal or isoelectronic tricarbonylmetalates which differ by the nature of the metal or of the π-bonded ring, the phenylcyclopentadienyl- ( 6 ), phenylborole- ( 7 ), , boratanaphthalene- ( 8 ), and boratabenzene- ( 9 ) , metalates led to a remarkable bonding diversity in a family of planar, centrosymmetric Pd 2 m 2 heterotetranuclear clusters, 10 – 15 , respectively. Whereas in 10 , 11 , and 13 , the π-bonded 5-electron donor ring interacts solely with the molybdenum atom, it bridges a Mo–Pd bond in 14 (via the adjacent π-system) and in 15 (via the B–N­( i Pr) 2 moiety) .…”

“…An example of bridging behavior of 5 involving the molybdenum and the nitrogen atoms was found with the structurally characterized dinuclear complex [Pt­{Mo­(η 5 -C 5 H 4 NMe 2 )(CO) 3 }­(NCPh)­Cl] ( 16 ), in which the amino ring substituent interacts with the adjacent platinum center …”

Synthesis of functional heterometallic complexes and clusters containing molybdenum and palladium or platinum, their self-assembly on gold surfaces and X-ray photoelectron spectroscopic studies

“…It was shown to adopt a planar, triangulated centrosymmetric structure analogous to that of cluster 1 [57]. [68] and trans-[Pt{Mo(h 5 -C 5 H 4 "-NMe 2 )(CO) 3 } 2 (NCPh) 2 ] (MoePteMo) [68] in which the cyclopentadienyl was functionalized with a dimethylamino group.…”

Boron, aluminium, gallium, indium and thallium

“…75 The boratabenzene complex [Mo(Z 6 -3,5-Me 2 C 5 B(N i Pr 2 )H 3 )(CO) 3 ] À has been described and the subsequent reaction chemistry with [AuCl(PPh 3 )] and 1 or 2 equivalents of HgCl 2 reported. 76…”