The synthesis of some polyether bridged diphosphines and their reaction with Rh(COD)acac

Abstract

The polyether bridged diphosphines,(n = 1,2) have been prepared in 60-70% yield by reduction of the corresponding diphosphinedioxides with SizCls or (i-Bu)zAIH. These diphosphinedioxides have been prepared in 75-90% yield by reaction of two equivalents of the appropriatewith one equivalent of di-and triethylene glycol ditosylate.In general, reaction between the diphosphines, Rh(COD)acac and HCIO1, gives a mixture of species, cis-[Rh(COD)(P P)] [C104] being the main complex. This complex reacts with CO to q3-transuwCOHP~P)I w41.

Transition-Metal Complexes Containing trans-Spanning Diphosphine Ligands

“…Timmer and Thewissen obtained similar products as they investigated the reaction between Rh(acac)(COD), CO, and several trans -spanning phosphinoether linkages Ph 2 P−( o- C 6 H 4 O((CH 2 ) 2 O) 2 - o- C 6 H 4 )PPh 2 , Ph 2 P−( o- C 6 H 4 O((CH 2 ) 3 O) 2 - o- C 6 H 4 )PPh 2 , and Me(Ph)P−( o- C 6 H 4 O((CH 2 ) 2 O) 2 - o- C 6 H 4 )P(Ph)Me to form η 3 - trans -[Rh(CO)(phosphinoether)] + complexes . Like Alcock and co-workers, the authors propose that these phosphinoether ligands are bound to the rhodium metal center through the trans -phosphorus atoms as well as the ether oxygen (which is trans to the carbonyl) based on infrared and NMR spectroscopic studies …”

“…In the former complex, the P(1)-Rh-P(2) bond angle of 165.9(1)°is indicative of an in-plane distortion, while in the latter complex, the P(1)-Rh-P(2) angle of 174.3(1)°indicates less strain. 64 For the trans-[Rh{PPh 2 (CH 2 ) 2 (OCH 2 CH 2 )-PPh 2 }(CO)] + complex, the dominant feature governing the structure of the bicyclic ring system is the 65 Like Alcock and co-workers, the authors propose that these phosphinoether ligands are bound to the rhodium metal center through the trans-phosphorus atoms as well as the ether oxygen (which is trans to the carbonyl) based on infrared and NMR spectroscopic studies. 65 When n ) 1, the PPh 2 (CH 2 ) 2 (OCH 2 CH 2 ) n PPh 2 ligand coordinated to rhodium(I) as a terdentate ligand by donating both phosphorus atoms and the oxygen atom.…”

“…64 For the trans-[Rh{PPh 2 (CH 2 ) 2 (OCH 2 CH 2 )-PPh 2 }(CO)] + complex, the dominant feature governing the structure of the bicyclic ring system is the 65 Like Alcock and co-workers, the authors propose that these phosphinoether ligands are bound to the rhodium metal center through the trans-phosphorus atoms as well as the ether oxygen (which is trans to the carbonyl) based on infrared and NMR spectroscopic studies. 65 When n ) 1, the PPh 2 (CH 2 ) 2 (OCH 2 CH 2 ) n PPh 2 ligand coordinated to rhodium(I) as a terdentate ligand by donating both phosphorus atoms and the oxygen atom. 64 When n ) 3, the ligand formed a loose chain with a tightly held water molecule encapsulated in the large ring.…”

Conformationally Restrained Octahedral Metallacrown Ethers with 1,2-(Ph2P(CH2CH2O)2)2C6H4 Ligands. X-ray Crystal Structure of cis-Mo(CO)4{1,2-(Ph2P(CH2CH2O)2)2C6H4-P,P‘}

“…Metallacrown ethers are a unique class of transition-metal complexes that are formed when α,ω-bis(phosphorus donor)−polyether ligands chelate transition metals. − Metallacrown ethers that contain the conformationally mobile Ph 2 P(CH 2 CH 2 O) 4 CH 2 CH 2 PPh 2 ( 1 ) ligand exhibit a variety of phosphine coordination geometries. These geometries include cis-octahedral ( cis -Mo(CO) 4 {Ph 2 P(CH 2 CH 2 O) 4 CH 2 CH 2 PPh 2 - P,P ‘} ( 2 ) 4 ), trans-octahedral ( trans -Mo(CO) 4 {Ph 2 P(CH 2 CH 2 O) 4 CH 2 CH 2 PPh 2 - P,P ‘} ( 3 ) 6 and cis , cis , trans -RuCl 2 (CO) 2 {Ph 2 P(CH 2 CH 2 O) 4 CH 2 CH 2 PPh 2 - P,P ‘} ( 4 ) 7 ), and cis-square planar ( cis -PtCl 2 {Ph 2 P(CH 2 CH 2 O) 4 CH 2 CH 2 PPh 2 - P,P ‘} ( 5 ) 5 ).…”

Modified methods to synthesize of 1,8-bis[2-(diphenylphosphoryl)phenoxy]-3,6-dioxaoctane (L). Crystal structure and vibration spectra of [LiL]ClO4·2C6H6

“…For the first time, phosphoryl podand L was synthesized by the reaction of sodium 2-diphenylphosphoryl phenolate with triethylene glycol ditosylate in boiling dioxane [6] or DMF [7]. Podand L 1 was prepared by the analogous reaction of sodium diphenylphosphorylmethyl phenolate with triethylene glycol ditosylate in dioxane [8].…”