Bis(di-t-butylphosphino)methane complexes of rhodium: homogeneous alkyne hydrosilylation by catalyst-dependent alkyne insertion into RhSi or RhH bonds. Molecular structures of the dimer [(dtbpm)RhCl]2 and of the silyl complex (dtbpm) Rh[Si(OEt)3](PMe3)

In Situ Synthesis of Neutral Dinuclear Rhodium Diphosphine Complexes [{Rh(diphosphine)(μ2‐X)}2]: Systematic Investigations

“…The bite angles (P-Rh-P) fall in the range between 75.23(10)8 for the bidentate ligands in [{Rh-(DtBPM)(m 2 -Cl)} 2 ] (YUWFEB; DtBPM = bis(di-tert-butylphosphino)methane) [48] and 100.29(4)8 in [{Rh(DiPPF)(m 2 -Cl)} 2 ]. The bite angles in the seven-membered chelated complexes that contain BINAP, SEGPHOS, and BICP are around 908.…”

Well‐Defined and Robust Rhodium Catalysts for the Hydroacylation of Terminal and Internal Alkenes

“…Hydroacylation of an oncyclic enol ether was also efficient and displayed the same sense of regiocontrol as the cyclic counterparts (entry 10). Hydroacylation of a,b-unsaturated esters could be achieved in an efficient, regioselective fashion, although the cinnamate example was less reactive (entries [11][12][13][14]. The regiocontrol observed for the ester series of substrates is in contrast (electronically) to that observed with the enol ether substrates,and is the subject of further investigation.…”

“…[3a,8] Wide-bite-angle,o rs terically bulky,l igands have this effect, but also change the ratio of alkene versus aldehyde hydroacylation [9] or the linear/branched selectivity. [10] Additionally,these systems in general still require high loadings,a nd activated alkenes or terminal alkynes as substrates.S mall-bite-angle phosphine ligands,R 2 PCH 2 PR 2 (e.g.,R= t Bu, Cy), initially developed by Hofmann et al, [11] have been shown to favor the products of reductive elimination [12] and we recently demonstrated that catalyst systems exemplified by [Rh(R 2 PCH 2 PR 2 )(h 6 -C 6 H 5 F)][BAr F 4 ][ R = t Bu, 1;A r F = 3,5-C 6 H 3 (CF 3 ) 2 ]c an be used at low catalyst loadings (e.g., 0.1 mol %) to couple terminal and activated internal alkenes with b-substituted aldehydes. [13] However, challenging internal alkenes are still out of reach with this system, as decarbonylation now outruns productive turnover.…”

Organometallic chemistry

“…His research interests combined all three fields, with a focus on homogeneous catalysis with transition metal complexes. Bidentate donor ligands with a small bite angle such as bis(di- tert -butylphosphino)methane (dtbpm) were a unique feature of his work [61,67,70–72 80–81 84,86,93–94 97,100–101 103,107,124,128,148–149] that ultimately enabled C–Si activation of organosilanes and the C–C activation of oxiranes by coordinatively unsaturated platinum species [66,149]. In the mechanism of the Dötz reaction, he found that chromacyclobutene structures were unrealistic intermediates and instead proposed vinylcarbene complexes as much more stable isomers [64,68,88].…”