TY - JOUR
T1 - Synthesis of 1,3-azaphosphol-2-ones. Crystal and molecular structures of [SP-4-2]-dichlorobis(3-phenyl-1,3-dihydrobenzo[1,3]azaphosphol-2-one-P) palladium(ii) and its chloro(methyl)platinum(ii) analogue
AU - Bennett, Justine
AU - Doyle, Roy J.
AU - Lee, Hwi Young
AU - Lu, Di
AU - Salem, Geoffrey
AU - Speldewinde, David J.
AU - Tifan, Michelle
AU - Willis, Anthony C.
PY - 2010
Y1 - 2010
N2 - Reaction of secondary phosphine (±)-(2-aminophenyl)phenylphosphine, (±)-app, with PCl5 in toluene gives the hydrochloride salt of the expected chlorophosphine (±)-(2-aminophenyl)chlorophenylphosphine, (±)-acpp.HCl, however, this is not the case with triphosgene. Rather the first example of a 1,3-azaphosphol-2-one is isolated, viz. (±)-3-phenyl- 1,3-dihydrobenzo[1,3]azaphosphol-2-one, (±)-pbap. The hydrochloride salt (±)-acpp.HCl readily reacts with excess vinyl-, 2-methylphenyl- or 2-methoxyphenyl magnesium bromide to give the corresponding tertiary phosphines (±)-(2-H2NC6H4)PPhR (where R = CHCH 2, 2-C6H4Me or 2-C6H 4OMe). Hydrophosphination of the vinyl substituted tertiary phosphine with (±)-app in the presence of KOBut provides a synthetic route to the elusive P2N2 quadridentate ligand (R P*,RP*)- and (RP* ,S P*)-(CH2)2 (PPhC6 H 4NH2-2)2, albeit in low yield. The azaphospholone (±)-pbap can be readily deprotonated with KOBut in thf and subsequently alkylated with methyl iodide or benzyl bromide to give the analogous N-methyl or N-benzyl derivatives. Alkylation with 1,3-dibromopropane gives the bis(azaphospholone) (RP*,R P*)- and (RP*,SP*)-1,3-bis[1- {3-phenyl-1,3-dihydrobenzo[1,3]azaphosphol-2-one}]propane. The latter and the N-methyl substituted azaphospholone can also be synthesised by the reaction of the corresponding secondary phosphine, viz. (RP*,R P*)- and (RP*,SP*)-(CH 2)3(NHC6H4PHPh-2)2 and (±)-(2-methylaminophenyl)phenylphosphine, with triphosgene. All three azaphospholones react with [PtClMe(1,5-cyclooctadiene)] in thf to give complexes of the type cis-[PtClMeL2] in which ligand L is coordinated via the P atom of the azaphospholones. The ligand (±)-pbap has also been complexed to palladium(ii) via the reaction with Li2[PdCl 4] in methanol to give cis-[PdCl2{(±)-pbap} 2]. The structures of cis-[PtClMe{(±)-pbap}2] and cis-[PdCl2{(±)-pbap}2] have been confirmed by X-ray analysis.
AB - Reaction of secondary phosphine (±)-(2-aminophenyl)phenylphosphine, (±)-app, with PCl5 in toluene gives the hydrochloride salt of the expected chlorophosphine (±)-(2-aminophenyl)chlorophenylphosphine, (±)-acpp.HCl, however, this is not the case with triphosgene. Rather the first example of a 1,3-azaphosphol-2-one is isolated, viz. (±)-3-phenyl- 1,3-dihydrobenzo[1,3]azaphosphol-2-one, (±)-pbap. The hydrochloride salt (±)-acpp.HCl readily reacts with excess vinyl-, 2-methylphenyl- or 2-methoxyphenyl magnesium bromide to give the corresponding tertiary phosphines (±)-(2-H2NC6H4)PPhR (where R = CHCH 2, 2-C6H4Me or 2-C6H 4OMe). Hydrophosphination of the vinyl substituted tertiary phosphine with (±)-app in the presence of KOBut provides a synthetic route to the elusive P2N2 quadridentate ligand (R P*,RP*)- and (RP* ,S P*)-(CH2)2 (PPhC6 H 4NH2-2)2, albeit in low yield. The azaphospholone (±)-pbap can be readily deprotonated with KOBut in thf and subsequently alkylated with methyl iodide or benzyl bromide to give the analogous N-methyl or N-benzyl derivatives. Alkylation with 1,3-dibromopropane gives the bis(azaphospholone) (RP*,R P*)- and (RP*,SP*)-1,3-bis[1- {3-phenyl-1,3-dihydrobenzo[1,3]azaphosphol-2-one}]propane. The latter and the N-methyl substituted azaphospholone can also be synthesised by the reaction of the corresponding secondary phosphine, viz. (RP*,R P*)- and (RP*,SP*)-(CH 2)3(NHC6H4PHPh-2)2 and (±)-(2-methylaminophenyl)phenylphosphine, with triphosgene. All three azaphospholones react with [PtClMe(1,5-cyclooctadiene)] in thf to give complexes of the type cis-[PtClMeL2] in which ligand L is coordinated via the P atom of the azaphospholones. The ligand (±)-pbap has also been complexed to palladium(ii) via the reaction with Li2[PdCl 4] in methanol to give cis-[PdCl2{(±)-pbap} 2]. The structures of cis-[PtClMe{(±)-pbap}2] and cis-[PdCl2{(±)-pbap}2] have been confirmed by X-ray analysis.
UR - http://www.scopus.com/inward/record.url?scp=72149122128&partnerID=8YFLogxK
U2 - 10.1039/b916913j
DO - 10.1039/b916913j
M3 - Article
SN - 1477-9226
VL - 39
SP - 256
EP - 264
JO - Dalton Transactions
JF - Dalton Transactions
IS - 1
ER -