Cyclo-Tetrakis(μ-diphenylphosphido)-1,5-bis(tri-tert-butylphosphine)-Tetracopper

Abstract

Copper phosphido compound Cu4(μ-PPh2)4(PtBu3)2 was synthesized by three synthetic methods and structurally characterized by X-ray diffraction and 1H, 31P, 13C and 31P HMBC NMR spectroscopy. Cu4(μ-PPh2)4(PtBu3)2 was also demonstrated to be a hydrophosphination pre-catalyst.

Halide-bridged tetranuclear organocopper(i) clusters supported by indolyl-based NCN pincer ligands and their catalytic activities towards the hydrophosphination of alkenes

“…Based on our experiments, and referring to the previous works, 57,73 a possible mechanism for the hydrophosphination of alkenes was proposed (Scheme 3). First, the tetranuclear Cu (I) cluster was dissociated by Ph 2 PH to give HL-Cu(I)-phosphido as an active species (I) in the catalysis, which was observed by 1 H NMR.…”

Divergent Mechanistic Pathways for Copper(I) Hydrophosphination Catalysis: Understanding that Allows for Diastereoselective Hydrophosphination of a Tri-substituted Styrene

“…37 Solution behavior of 1 under these conditions is consistent with [(Ph2PH)CuPPh2]n. The copper(I) compound [(PPh3)CuH]6, 37 which is a precursor to (PPh3)CuPPh2 upon treatment with Ph2PH, 38 was also an effective precatalyst. Prior study of copper compounds in hydrophosphination catalysis are consistent with these observations, 16,25,26,37,[39][40][41][42][43] but the observation of successful hydrophosphination of unactivated alkenes with 1 is unique among that series and tied to photocatalytic conditions. That reactivity indicates that the operant mechanism of P-C bond formation is migratory insertion.…”

“…With data to support a soluble, closed-shell process and generalizable copper photocatalysis, a suitable molecular model system was pursued to provide greater understanding of this catalysis. Such a discrete molecular compound catalyst is attractive because polymetallic copper phosphido compounds have also been demonstrated to be effective pre-catalysts for this hydrophosphination 41,43 but are more challenging for study. To identify a discrete copper(I) phosphido compound for further study, several catalytic reactions were attempted with the known derivative IPrCuPPh2 (9) (Table 3).…”

Divergent Mechanistic Pathways for Copper(I) Hydrophosphination Catalysis: Understanding that Allows for Diastereoselective Hydrophosphination of a Tri-substituted Styrene

“…With data to support a soluble, closed-shell process and generalizable copper photocatalysis, a suitable molecular model system was pursued to provide greater understanding of this catalysis. Such a discrete molecular compound catalyst is attractive because polymetallic copper phosphido compounds have also been demonstrated to be effective pre-catalysts for this hydrophosphination 42,44 but are more challenging for study. To identify a discrete copper(I) phosphido compound for further study, several catalytic reactions were attempted with the known derivative IPrCuPPh2 (9) (Table 4).…”

“…38 Solution behavior of 1 under these conditions is consistent with [(Ph2PH)CuPPh2]n. The copper(I) compound [(PPh3)CuH]6, 38 which is a precursor to (PPh3)CuPPh2 upon treatment with Ph2PH, 39 was also an effective precatalyst. Prior study of copper compounds in hydrophosphination catalysis are consistent with these observations, 16,25,26,38,[40][41][42][43][44][45][46][47] but the observation of successful hydrophosphination of unactivated alkenes with 1 is unique among that series and tied to photocatalytic conditions. That reactivity indicates that the operant mechanism of P-C bond formation is migratory insertion.…”