Flexible Building Blocks for Transition Metal Early−Late Chemistry. Synthesis of Heterobimetallic Tetranuclear Metallomacrocycles

Abstract

The crystal structures of the 16-membered metallomacrocycles 7 and 9 have been determined by X-ray diffraction and show a rhomboidal arrangement of the metal centers with a conformation that is largely determined by steric grounds.3

Early–Late Heterometallic Complexes of Gold and Zirconium: Photoluminescence and Reactivity

“…The zirconium‐oxygen bond lengths are both 1.998(2) Å, and are similar in length to other zirconocene alkoxides . The O1‐Zr1‐O1′ bond angle (96.71(13)°) differs slightly from an ideal tetrahedral angle, so the coordination geometry of the zirconium centre can be best described as distorted tetrahedral.…”

“…The zirconium-oxygen bond lengths are both 1.998 (2) , and are similar in length to otherz irconocene alkoxides. [16,36] The O1-Zr1-O1' bond angle (96.71(13)8)d iffers slightly from an ideal tetrahedral angle, so the coordinationg eometry of the zirconium centrec an be best described as distorted tetrahedral. The cyclopentadienyl rings coordinate to the metal in as taggered conformation, with carbonÀzirconium bond lengths from 2.480(3) to 2.543 (4) .…”

New rhodium(I) supramolecular structures containing pyridyl and bipyridyl ligands

“…However, other metals have also been used in these reactions. In particular, Rh(I) and Ir(I) units have been explored in the synthesis of bi- [23][24][25][26][27] and three-dimensional compounds [28,29] and they are of great interest due to their potential catalytic activity and luminescent behaviour, that could be very useful in host-guest studies [30][31][32][33][34][35].…”

Bridged Dinuclear Tripodal Tris(amido)phosphane Complexes of Titanium and Zirconium as Diligating Building Blocks for Organometallic Polymers

“…The target bis-(phosphane) building blocks for such an approach are shown in Scheme 1, and feature a pair of metal-bearing tripodal tris(amido)phosphane ligands, as well as a bridge between the metal centers labeled M. The addition of suitable late-transition-metal fragments capable of bonding to two phosphane moieties, labeled MЈL n in Scheme 1, should provide a facile route to transition-metal-containing oligomers and polymers. Although there are a plethora of examples of bis(phosphanes) used as bridging ligands, [22][23][24] as well as flexible ligands incorporating hard and soft donors that have been utilized as building blocks for bimetallic and polynuclear early-late transition-metal clusters, [25,26] the complexes we propose here could provide rare examples of linear bis(phosphane) building blocks, [27][28][29][30][31][32] where throughspace interactions provide the potential for extended interactions. In this paper, we test the synthetic feasibility of preparing such building blocks using the diamagnetic early transition metals zirconium and titanium, with the goal of introducing redox active and paramagnetic metal-bridge fragments in future endeavours.…”