A versatile strategy for the formation of hydride-bridged actinide–iridium multimetallics

Abstract

Reaction of the potassium pentamethylcyclopentadienyl iridate trihydride K[IrCp*H3] with UCl4 and ThCl4(DME)2 led to the complete replacement of the halide ligands to generate multimetallic complexes U{(μ-H)3IrCp*}4 (1) and Th{[(μ-H2)(H)IrCp*]2[(μ-H)3IrCp*]2} (2),...

Photolysis-driven bond activation by thorium and uranium tetraosmate polyhydride complexes

“…38 The Os centers are slightly distorted from an ideal tetrahedral geometry around Th, with a s 4 value 39 of 0.93 (calculated with a = 115.80(2)°, b = 112.32(2)°), slightly less than that of A (0.97). 31 The Os-Os distances range from 4.7446(7) Å to 5.1395(7) Å, which precludes any Os-Os interactions considering osmium's covalent radius of 1.44 Å. 38 bridging hydrides around the thorium center, matching the highest observed coordination number around an atom in an isolated compound; 40,41 interestingly, higher coordination numbers have been proposed for early actinide-noble gas complexes.…”

Alkane Elimination Preparation of Heterobimetallic MoAl Tetranuclear and Binuclear Complexes Promoting THF Ring Opening

“…The reaction of triisobutylaluminum with complex Cp*Mo(CO) 3 H in n-pentane at 35 As part of our ongoing research focus on designing novel heterobimetallic architectures [26,28,[34][35][36][37], we thus chose to explore the reactivity of alkylaluminum reagents with transition metal hydrides, hopping to trigger alkane elimination reactions. Prior work within our group has demonstrated the capability of an iridium polyhydride complex, Cp*IrH4, to react with isobutyl aluminum derivatives, yielding heterobimetallic assemblies.…”

“…An alternative proficient strategy to synthesize heterobimetallic complexes involves the alkane elimination reaction [24][25][26][27][28] between a transition metal hydride derivative and alkyl aluminum reagents [9,10,[29][30][31][32][33]. This reaction can be conceptualized as an electrophilic hydride abstraction process.…”

Cooperative activation of carbon–hydrogen bonds by heterobimetallic systems

“…5). [59][60][61][62][63] Such systems are, by virtue of the principle of microscopic reversibility, particularly well poised to promote the reverse reaction, i.e. the heterolytic cleavage of C-H bonds through unusual cooperative metal-metal pathways (Fig.…”

“…5 Alkane elimination synthesis of heterobimetallic species, exemplified on a Ta/Ir complex. [59][60][61][62][63] Fig. 6 Catalytic performances of Ta/Ir species in an arene hydrogen isotope exchange reaction between C 6 D 6 and fluorobenzene.…”