Metal(II) template assisted syntheses of two P―C―O―P chelating ligands incorporating a bulky 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantyl cage

Controlled stepwise reaction of a geminal substituted alkene or primary amine group afforded a small library of new functionalised tertiary and ditertiary phosphines. Accordingly, Mannich based condensation of the commercially available disubstituted arene C 6 H 4 (NH 2){2-C(Me)=CH 2 } with HOCH 2 PR 2 (R 2 = Cg: 1,3,5,7-tetramethyl-2,4,8-trioxa-6phosphaadamantyl; Ph 2) afforded the (aminomethyl)phosphines C 6 H 4 (NHCH 2 PCg){2-C(Me)=CH 2 } L 1 and C 6 H 4 (NHCH 2 PPh 2){2-C(Me)=CH 2 } L 2 in approx. 60% yield. In addition to the formation of L 2 , the diphosphine L 3 was also identified and independently synthesised upon reaction of C 6 H 4 (NH 2){2-C(Me)=CH 2 } with two equiv. of HOCH 2 PPh 2 in CH 3 OH under reflux. Alternatively, reaction of C 6 H 4 (NH 2){2-C(Me)=CH 2 } with H-PR 2 (R 2 = Cg or Ph 2) in the presence of AIBN [2,2`-azobis(2-methylpropionitrile)] as free radical initiator, afforded the primary amine functionalised phosphines C 6 H 4 (NH 2){2-CH(Me)CH 2 PCg} L 4 and C 6 H 4 (NH 2){2-CH(Me)CH 2 PPh 2 } L 5 in 85% and 66% isolated yields respectively. In both cases only the anti-Markovnikov addition products were observed. Subsequent reaction of L 5 with HOCH 2 PR 2 (R 2 = Ph 2) afforded the unsymmetrical ditertiary phosphine C 6 H 4 (NHCH 2 PPh 2){2-CH(Me)CH 2 PPh 2 } L 6. Some preliminary coordination studies towards [RuCl(µ-Cl)(η 6-C 10 Η 14)] 2, [AuCl(tht)] (tht = tetrahydrothiophene) and [MCl 2 (η 4-cod)] (M = Pd, Pt; cod = cycloocta-1,5-diene) demonstrate these new ligands behave as classic P-donors leaving the pendant amino or alkenyl groups non-coordinating. All compounds have been characterised by multinuclear NMR, FT−IR, mass spectrometry and microanalysis. Single crystal X-ray studies have been performed on L 3 , L 5 , L 6 , 1, 3b•0.5CH 2 Cl 2 , 4a•1.5CH 2 Cl 2 , 5 and 6•0.5CDCl 3 •0.5C 4 H 10 O

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New (aminomethyl)phosphines via selective hydrophosphination and/or phosphorus based Mannich condensation reactions

Cao

Elsegood

Lastra-Calvo

et al. 2017

Journal of Organometallic Chemistry

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Phosphines and related P–C‐bonded compounds

Allen

2013

Organophosphorus Chemistry

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This chapter reviews the literature published during 2011 relating to the above area, apart from a few papers from 2010 in less accessible journals which came to light in Chemical Abstracts in 2011. Synthetic routes to phosphines are reported, together with studies of their reactivity towards various atomic and molecular electrophilic sites involving carbon, halogen, boron, nitrogen and other acceptors. Also reported are studies of developments in the chemistry of low coordination number pπ-bonded phosphorus compounds and related potentially aromatic heterocyclic phosphorus systems.

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Organodiphosphines in cis-Pt(η²-PX_nP)(Cl)₂ (n = 1,2,3) derivatives: Structural aspects

Melník,

Mikuš

2024

Main Group Metal Chemistry

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This article covers almost 130 Pt(ii) complexes with an inner coordination sphere of cis-PtP2Cl2. The P-donor ligands are organodiphosphines that create four-, five-, and six-membered metallocyclic rings. There are two types of four-membered rings: PCP and PNCP, and four types of five-membered rings: PC–CP, PC═CP, PNNP, and PCOP. There are wide varieties of the six-membered metallocyclic rings: PC3P (most common), PCNCP, PCSCP, PCSiCP, PNCNP, PCCOP, PCCNP, POPNP, POSiOP, P(CNC)2P, and P(CNC)(CCC)P. The P–Pt–P bite angles open with the size of the metallocyclic rings in the order (total mean values 72.4° [PXP] < 86.4° [PXXP] < 94.0° [PXXNP]). There are complexes that are examples of distortion and ligand isomerism. The structural data are analyzed and discussed.

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Metal(II) template assisted syntheses of two P―C―O―P chelating ligands incorporating a bulky 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantyl cage

Cited by 3 publications

References 22 publications

New (aminomethyl)phosphines via selective hydrophosphination and/or phosphorus based Mannich condensation reactions

New (aminomethyl)phosphines via selective hydrophosphination and/or phosphorus based Mannich condensation reactions

Phosphines and related P–C‐bonded compounds

Organodiphosphines in cis-Pt(η²-PX_nP)(Cl)₂ (n = 1,2,3) derivatives: Structural aspects

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Metal(II) template assisted syntheses of two P―C―O―P chelating ligands incorporating a bulky 1,3,5,7-tetramethyl-2,4,8-trioxa-6-phosphaadamantyl cage

Cited by 3 publications

References 22 publications

New (aminomethyl)phosphines via selective hydrophosphination and/or phosphorus based Mannich condensation reactions

New (aminomethyl)phosphines via selective hydrophosphination and/or phosphorus based Mannich condensation reactions

Phosphines and related P–C‐bonded compounds

Organodiphosphines in cis-Pt(η2-PX n P)(Cl)2 (n = 1,2,3) derivatives: Structural aspects

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Organodiphosphines in cis-Pt(η²-PX_nP)(Cl)₂ (n = 1,2,3) derivatives: Structural aspects