Linking Multiple Bonds between Metal Atoms:  Clusters, Dimers of “Dimers”, and Higher Ordered Assemblies

Tuning the electronic structure of Mo–Mo quadruple bonds by N for O for S substitution

“…16,17 Investigations by Chisholm and coworkers on the photoexcited states of trans-[M 2 (TiPB) 2 (O 2 CR) 2 ] (R = 2-thiophene 18,19 or C 6 H 4 -4-CN; TiPB = 2,4,6-triisopropylbenzoate) 20 show emission from T 1 states that are about the dimetal core also makes MM multiply bonded paddlewheel compounds good candidates for incorporation into materials with potentially interesting optoelectronic properties. [21][22][23][24][25][26][27] This was highlighted in a detailed study by Zhou and co-workers which demonstrated that the shape and size of molecular architectures formed using dicarboxylate ligands to bridge Mo 2 4+ units can be controlled by tuning the bridging angle and size of the bridging dicarboxylate ligand. 28 Changing the nature of the three atom ligand bridging the M 2…”

New diruthenium complexes formed via modification with 1,1′-ferrocene dicarboxylic acid

“…Exploration of electronic interactions along the equatorial directions of dinuclear paddlewheel compounds has attracted intense interest during the last two decades [1][2][3][4][5][6][7][8]. The variety of such complexes includes compounds that link one dinuclear center to another dinuclear center, often in an attempt to determine a pathway of electronic communication between the bridged redox centers [1][2][3][4][5]9].…”

“…The variety of such complexes includes compounds that link one dinuclear center to another dinuclear center, often in an attempt to determine a pathway of electronic communication between the bridged redox centers [1][2][3][4][5]9]. Work pioneered by Cotton and Chisholm gave rise to the ''dimer of dimers'', where two M 2 (M = Mo and W) units were linked by dicarboxylates [1,2,4,9,10].…”

“…The variety of such complexes includes compounds that link one dinuclear center to another dinuclear center, often in an attempt to determine a pathway of electronic communication between the bridged redox centers [1][2][3][4][5]9]. Work pioneered by Cotton and Chisholm gave rise to the ''dimer of dimers'', where two M 2 (M = Mo and W) units were linked by dicarboxylates [1,2,4,9,10]. The dependence of electronic couplings on the chemical nature and length of the bridging ligand was elaborated upon extensively [3,[11][12][13], and the highly delocalized ''dimer of dimers'' based on W 2 are most noteworthy [14][15][16].…”

“…In addition, activities in catalytic oxygenation and C-H insertion by Ru 2 compounds have been uncovered during the recent years [17][18][19]. Work from our laboratory and others demonstrated both the strong intermetallic couplings mediated by the polyyne-diyl chains [20][21][22], and across the Ru 2 (DArF) 4 and Ru 3 (dpa) 4 core along the axial directions [23][24][25][26]. On the other hand, the intermetallic electronic interaction was not detected in a dimer of Ru 2 compounds that are linked along the equatorial directions [27].…”