{CH₂(PPh₂=NSiMe₃)(PPh₂=S)} and {CH(PPh₂=NSiMe₃)(Ph₂P=S)}^– as Ligands in Zinc Chemistry: Synthesis and Structures

Abstract

The (iminophosphoranyl)(thiophosphoranyl)methane zinc complexes [{(PPh2=NSiMe3)(PPh2=S)CH2}ZnX2] (X = Cl, I) have been obtained by the reaction of {CH2(PPh2=NSiMe3)(PPh2=S)} with the corresponding zinc dihalides ZnCl2 and ZnI2. The (iminophosphoranyl)(thiophosphoranyl)methane ligand coordinates as a bidentate ligand through the nitrogen and sulfur atoms to the zinc atom to form a six‐membered metallacycle (N–P–C–P–S–Zn). The reaction of {CH2(PPh2=NSiMe3)(PPh2=S)} with [Zn{N(SiMe3)2}2] and ZnPh2 resulted in the (iminophosphoranyl)(thiophosphoranyl)methanide complexes [{(PPh2=NSiMe3)(PPh2=S)CH}Zn{N(SiMe3)2}] and [{(PPh2=NSiMe3)(PPh2=S)CH}ZnPh], respectively. In addition to the coordination of the phosphinimine nitrogen and sulfur atoms to the zinc atom, a long contact between the methine carbon atom of the P–C–P bridge and the zinc atom was observed in these complexes. The solid‐state structures of all the new compounds were established by single‐crystal X‐ray diffraction.

The Benzoyl‐Coenzyme A Reductase and 2‐Hydroxyacyl‐Coenzyme A Dehydratase Radical Enzyme Family

“…In 2009 So and co‐workers described the synthesis of the neutral ligand 1c and its deprotonation with n BuLi and t BuLi to give 3c and 2c , respectively 8. P. Roesky et al have used potassium reagent K 3c to prepare a variety of lanthanide complexes by metathesis; lanthanide complexes were also obtained from the neutral ligand 1c and lanthanide amides by means of amine elimination9,10 The same group has also described zinc complexes of neutral ligand 1c and monoanion 3c 11. In all the lanthanide and zinc complexes, methanide ligand 1c engages in N,S ‐coordination, and there is an additional long contact between the metal center and the carbon atom of the PCP unit 9–11…”

(Iminophosphoranyl)(thiophosphoranyl)methane rare-earth borohydride complexes: synthesis, structures and polymerization catalysis

“…Thus, the chloride complexes [{CH(PPh 2 NSiMe 3 ) 2 }-Ln{(Ph 2 P) 2 N}Cl] (Ln = Y, La, Nd, Yb) were shown to initiate the ring-opening polymerization (ROP) of ε-caprolactone (CL) and the polymerization of methyl methacrylate (MMA). 53,54 We reported the potassium reagent [K{CH(PPh 2 vNSiMe 3 )-(PPh 2 vS)}] 2 as well as its reactions with LnCl 3 , which led to the dichloro complexes [{CH(PPh 2 vNSiMe 3 )(PPh 2 vS)}-LnCl 2 (THF)] (Ln = Dy, Er). 47 For the ROP of CL, the narrowest dispersity values ever obtained from a rare-earth metal borohydride initiator were then measured (Đ M = 1.06 1.11).…”

“…37 The bisborohydride analogues, [{(CH(PPh 2 NSiMe 3 ) 2 }La(BH 4 ) 2 (THF)] and [{CH(PPh 2 NSiMe 3 ) 2 }Ln(BH 4 ) 2 ] (Ln = Y, Lu) were demonstrated as successful initiators for the ROP of CL 49 and trimethylene carbonate (TMC), 46 as well as for the polymerization of MMA. 53 54 The aromatic derivatives of phosphine( phosphinimino) methane CH 2 (PPh 2 vNAr)(Ph 2 PS) (Ar = p-tolyl, p-tolyl) and some platinum compounds were reported in the 1990s by Elsevier. 49 Recently, we have focused on the analogous (iminophosphoranyl)(thiophosphoranyl)methanide ligand {CH(PPh 2 vNR)-(Ph 2 PS)} − which is isoelectronic to the bis( phosphinimino)methanide ligand but has a hard and a soft donor atom.…”

“…49 Recently, we have focused on the analogous (iminophosphoranyl)(thiophosphoranyl)methanide ligand {CH(PPh 2 vNR)-(Ph 2 PS)} − which is isoelectronic to the bis( phosphinimino)methanide ligand but has a hard and a soft donor atom. 53,54 † Cif files of compounds 2-9. CCDC 1040816-1040823.…”

“…We reported the potassium reagent [K{CH(PPh 2 vNSiMe 3 )-(PPh 2 vS)}] 2 as well as its reactions with LnCl 3 , which led to the dichloro complexes [{CH(PPh 2 vNSiMe 3 )(PPh 2 vS)}-LnCl 2 (THF)] (Ln = Dy, Er). 53 54 The aromatic derivatives of phosphine( phosphinimino) methane CH 2 (PPh 2 vNAr)(Ph 2 PS) (Ar = p-tolyl, p-tolyl) and some platinum compounds were reported in the 1990s by Elsevier. 55 Lately, Cadierno and Gimeno reported on the aromatic derivatives CH 2 (PPh 2 vNAr)(Ph 2 PS) (Ar = 2,4,6-C 6 H 2 Me 3 , 4-C 6 F 4 CHO, 4-C 6 F 4 CN, and 4-C 5 F 4 N), which were coordinated as monoanionic ligands {CH(PPh 2 vNAr)(Ph 2 PS)} − to ruthenium.…”