Synthesis of Chalcogenidoimidodiphosphinato–Rh^I Complexes and DFT Investigation of Their Catalytic Activation in Olefin Hydroformylation

Abstract

The synthesis and spectroscopic characterization of [Rh{R 2 P(S)NP(S)R 2 -S,SЈ}(cod)] [cod = 1,5-cyclooctadiene; R = Ph (1), iPr (4)], [Rh{Ph 2 P(S)NP(S)Ph 2 -S,SЈ}(CO) 2 ] (2) and [Rh{Ph 2 P(S)NP(S)Ph 2 -S,SЈ}(CO)(PPh 3 )] (3) is described. The crystal structures of complexes 1 and 3 are also presented. The synthesized Rh I complexes are essentially not catalytically active against olefin hydroformylation, in contrast to the previously reported complex [Rh{Ph 2 P(O)NPPh 2 -P,O}(CO)-(PPh 3 )] (6). Differences in the catalytic activity were interpre-[a]

Investigating the Structural, Spectroscopic, and Electrochemical Properties of [Fe{(EPiPr2)2N}2] (E = S, Se) and the Formation of Iron Selenides by Chemical Vapor Deposition

“…The coordination chemistry of the dichalcogenidoimidodiphosphinato ligands R 2 P(E)NHP(E′)R′ 2 (LH; E, E′ = O, S, Se, Te; R, R ′ = alkyl or aryl groups) towards both main‐group and transition‐metal elements is rather versatile, especially in their anionic [R 2 P(E)NP(E′)R′ 2 ] – (L – ) form These ligands coordinate readily to divalent first‐row transition‐metal ions (M = Mn, Co, Zn) to afford tetrahedral complexes,, whereas both tetrahedral and square‐planar coordination spheres have been observed for Ni , . Only two [Fe{(SPR 2 ) 2 N} 2 ] complexes have been reported thus far.…”

Computational aspects of hydroformylation

“…Grigoropoulos and co-workers synthesised chalcogenidoimidodiphosphinato-Rh complexes and employed them in the hydroformylation of styrene. 91 The structure of the catalyst precursors were computed at BP86/TZVP level (Fig. 9).…”

Unusual 31P Hyperfine Strain Effects in a Conformationally Flexible Cu(II) Complex Revealed by Two-Dimensional Pulse EPR Spectroscopy

“…The coordination chemistry of the LH dichalcogenidoimidodiphosphinato ligands, R 2 P­(E)­NHP­(E′)­R′ 2 (E, E′ = O, S, Se, Te; R, R′ = alkyl or aryl groups), toward both main group and transition metal elements, has been shown to be remarkably versatile, especially in their anionic L – , R 2 P­(E)­NP­(E′)­R′ 2 – , form. − Interestingly, compared with the first row transition metal ions M­(II), M = Mn, Fe, Co, Ni, Zn, − a relatively smaller number of Cu­(II) complexes bearing this type of ligands has been reported to date. These include binuclear [Cu 2 {Ph 2 P­(O)­NP­(O)­Ph 2 -κ 2 O,O ′} 2 (μ-O 2 PPh 2 ) 2 ] and [Cu­(μ 2 -OH)­{Ph 2 P­(O)­NP­(O)­Ph 2 -κ 1 O,O ′}­(1,10-phen-κ 2 N,N ′)] 2 ·2H 2 O, as well as mononuclear complexes, such as [Cu­{R 2 P­(O)­NP­(O)­R 2 -κ 2 O,O ′} 2 ], R = OPh, Ph, and [Cu­{Ph 2 P­(S)­NP­(S)­Ph 2 } 2 ].…”