Cleaving bonds in CH₃OSO₂CF₃with [1,2,4-(Me₃C)₃C₅H₂]₂CeH; an experimental and computational study

Lanthanides and actinides: Annual survey of their organometallic chemistry covering the year 2013

“…Similarly, [53]. The room temperature C-N bond cleavage of anionic guanidinate ligands in rare-earth metal complexes has been reported.…”

Activation of SO2 and CO2 by Trivalent Uranium Leading to Sulfite/Dithionite and Carbonate/Oxalate Complexes

“…This reaction is, in fact, very reminiscent to that of [( Ar, t Bu N) 3 Ti(O)] − with CO 2 reported by Cummins and co‐workers 6. The only known metal sulfite complex in f‐element chemistry is [{(1,2,4‐(Me 3 C) 3 C 5 H 2 ) 2 Ce}(μ‐SO 3 )], which is isolated from a mixture of multiple products, all resulting from reaction of a cerium hydride precursor with CH 3 OSO 2 CF 3 7…”

“…All bond lengths, together with the cone angles (310.4/309.1°), fall within the range found for other bridging sulfite complexes described in the literature 4b. 7…”

“…[6] The only known metal sulfite complex in f-element chemistry is [{(1,2,4-(Me 3 C) 3 C 5 H 2 ) 2 Ce}(m-SO 3 )], which is isolated from a mixture of multiple products, all resulting from reaction of a cerium hydride precursor with CH 3 OSO 2 CF 3 . [7] The scarcity of reductive SO 2 activation chemistry clearly relates to its stability; and thus, is reminiscent to that of CO 2 . Intuitively, the transformation of SO 2 to SO 3 2À or S 2 O 4 2À is similar to the formation of CO 3 2À or C 2 O 4 2À from CO 2 but, to the best of our knowledge, absent from the current literature.…”

Crystal structures of twoansa-titanocene trifluoromethanesulfonate complexes bearing the Me2Si(C5Me4)2ligand

“…However, this binding mode is known for group 4 complexes (Giannini et al, 1997;Donkervoort et al, 1997;Basuli, Bailey et al, 2003;Basuli et al, 2004). Metallocene compounds such as the lanthanide compounds [C 5 H 3 (Hitchcock et al, 2006) and [C 5 H 2 (t-Bu) 3 ] 2 Ce( 2 O,O-OTf) (Werkema et al, 2013) have been reported as well. Compared to the above mentioned titanocene trifluoromethanesulfonate, which shows the trifluoromethanesulfonate ligand in 1 coordination, the Ti-O bonds are significantly longer in the title compound 1, pointing towards a much weaker coordination of the ligand in a symmetrical arrangement [for comparison: A: 2.078 (1), B: 2.058 (2) Å ].…”