Formation of Metallamacrocycles from Palladium(II), Platinum(II) and Copper(I) Complexes and the Ditopic Ligands [{p-(Ph2PO)C6H4}2CMe2], [{2-Ph2PO-3,5-(Me3C)2C6H2}2S], [{p-[(C10H6O)2PO]C6H4}2CMe2]

Abstract

The new ligands bis(phosphinito) [{2-Ph 2 PO-3,5-(Me 3 C) 2 C 6 H 2 } 2 S] (4) and chiral bis(phosphite) [{p-[(C 10 H 6 O) 2 PO]C 6 H 4 } 2 CMe 2 ] (5) were synthesised and their reactions with palladium(II), platinum(II), copper(I) substrates were studied. The ligand 3 [{p-(Ph 2 PO)C 6 H 4 } 2 CMe 2 ], previously reported by us, was also used in the same reactions. Ligands 3 and 5 formed 28-membered metallamacrocycles while ligand 4 afforded the analogous compound only in the reaction with the copper(I) substrate. In the reaction of 3 with [Pd(PhCN) 2 Cl 2 ] the metallamacrocycle [PdCl 2 (µ-3)] 2 (6) or the oligomer [Pd 2 Cl 4 (µ-3)] n (7) were formed, depending on the molar ratio used. The reaction of 3 with [Pd(η 3 -C 3 H 5 )Cl] 2 afforded compound {[Pd(η 3 -C 3 H 5 )Cl] 2 (µ-3)} (8). The allylpalladium macrocycle [Pd(η 3 -C 3 H 5 )(µ-3)] 2 [OTf] 2 (9) was obtained by treating a solution of 8 in THF with [a]

Semi-Rigid Bis-Phosphane Ligands for Metallamacrocycle Formation

“…We report here the efficient syntheses and complexing properties of two new semi‐rigid, ditopic bis‐phosphane ligands which further explore the relationship between ligand geometry and the structures of their transition metal complexes. The work extends recent reports on the formation of metallamacrocycles using related ligand types 11…”

Semi-Rigid Bis-Phosphane Ligands for Metallamacrocycle Formation

“…We report here the efficient syntheses and complexing properties of two new semi‐rigid, ditopic bis‐phosphane ligands which further explore the relationship between ligand geometry and the structures of their transition metal complexes. The work extends recent reports on the formation of metallamacrocycles using related ligand types 11…”

A Silsesquioxane-Based Diphosphinite Ligand: Synthesis, DFT Study, and Coordination Chemistry

“…The total sums of the angles around the phosphorus atoms, viewed along the Pt−P bonds, are 346.35° (P 1 ) and 343.64° (P 2 ). The Pt−P bond lengths (2.2290(7) Å for Pt−P 1 and 2.2372(8) Å for Pt−P 2 ) and the Pt−Cl bond lengths (2.3640(8) Å for Pt−Cl 1 and 2.3621(8) Å for Pt−Cl 2 ) are in their expected ranges, respectively, as reported for other platinum−phosphinite complexes. ,,,,, In the platinum−(silyl−diphosphinite) compound cis -[PtCl 2 SiPh 2 (OPPh 2 ) 2 ] ( B ), described by the group of Pringle, the P−O and Si−O bond lengths are 1.637 and 1.691 Å on average, respectively . In complex 6 , the P−O bond lengths are considerably shorter at 1.591(2) Å (P 1 −O 2 ) and 1.603(2) Å (P 2 −O 1 ).…”

“…The 31 P NMR spectrum of PtCl 2 ( 1 ) shows a single peak at δ 64.5 ppm, flanked by 195 Pt satellites and a coupling constant J Pt - P of 4246 Hz. This value is a clear indication of the cis coordination of the diphosphinite to the platinum center. ,,− The chemical shift difference with the uncoordinated ligand Δδ is 34.2 ppm upfield in the 31 P NMR spectrum, considerably more than that found from the reaction to yield complex 5 , where Δδ is only 5.9 ppm upfield. In the 13 C NMR spectrum, the characteristic signals for the ipso carbons of the cyclopentyl side groups appeared in the normal region, in a 1:1:1:2:2 ratio.…”

Chiral phosphites as ligands in asymmetric metal complex catalysis and synthesis of coordination compounds

“…Unusual binuclear metal complexes 120a,b containing twentyeight-membered macrocycles 193 should also be pointed out.…”

Semi-Rigid Bis-Phosphane Ligands for Metallamacrocycle Formation

“…We report here the efficient syntheses and complexing properties of two new semi‐rigid, ditopic bis‐phosphane ligands which further explore the relationship between ligand geometry and the structures of their transition metal complexes. The work extends recent reports on the formation of metallamacrocycles using related ligand types 11…”

A Silsesquioxane-Based Diphosphinite Ligand: Synthesis, DFT Study, and Coordination Chemistry

“…The total sums of the angles around the phosphorus atoms, viewed along the Pt−P bonds, are 346.35° (P 1 ) and 343.64° (P 2 ). The Pt−P bond lengths (2.2290(7) Å for Pt−P 1 and 2.2372(8) Å for Pt−P 2 ) and the Pt−Cl bond lengths (2.3640(8) Å for Pt−Cl 1 and 2.3621(8) Å for Pt−Cl 2 ) are in their expected ranges, respectively, as reported for other platinum−phosphinite complexes. ,,,,, In the platinum−(silyl−diphosphinite) compound cis -[PtCl 2 SiPh 2 (OPPh 2 ) 2 ] ( B ), described by the group of Pringle, the P−O and Si−O bond lengths are 1.637 and 1.691 Å on average, respectively . In complex 6 , the P−O bond lengths are considerably shorter at 1.591(2) Å (P 1 −O 2 ) and 1.603(2) Å (P 2 −O 1 ).…”

“…The 31 P NMR spectrum of PtCl 2 ( 1 ) shows a single peak at δ 64.5 ppm, flanked by 195 Pt satellites and a coupling constant J Pt - P of 4246 Hz. This value is a clear indication of the cis coordination of the diphosphinite to the platinum center. ,,− The chemical shift difference with the uncoordinated ligand Δδ is 34.2 ppm upfield in the 31 P NMR spectrum, considerably more than that found from the reaction to yield complex 5 , where Δδ is only 5.9 ppm upfield. In the 13 C NMR spectrum, the characteristic signals for the ipso carbons of the cyclopentyl side groups appeared in the normal region, in a 1:1:1:2:2 ratio.…”

Chiral phosphites as ligands in asymmetric metal complex catalysis and synthesis of coordination compounds

“…Unusual binuclear metal complexes 120a,b containing twentyeight-membered macrocycles 193 should also be pointed out.…”

Semi-Rigid Bis-Phosphane Ligands for Metallamacrocycle Formation

“…We report here the efficient syntheses and complexing properties of two new semi‐rigid, ditopic bis‐phosphane ligands which further explore the relationship between ligand geometry and the structures of their transition metal complexes. The work extends recent reports on the formation of metallamacrocycles using related ligand types 11…”

A Silsesquioxane-Based Diphosphinite Ligand: Synthesis, DFT Study, and Coordination Chemistry

“…The total sums of the angles around the phosphorus atoms, viewed along the Pt−P bonds, are 346.35° (P 1 ) and 343.64° (P 2 ). The Pt−P bond lengths (2.2290(7) Å for Pt−P 1 and 2.2372(8) Å for Pt−P 2 ) and the Pt−Cl bond lengths (2.3640(8) Å for Pt−Cl 1 and 2.3621(8) Å for Pt−Cl 2 ) are in their expected ranges, respectively, as reported for other platinum−phosphinite complexes. ,,,,, In the platinum−(silyl−diphosphinite) compound cis -[PtCl 2 SiPh 2 (OPPh 2 ) 2 ] ( B ), described by the group of Pringle, the P−O and Si−O bond lengths are 1.637 and 1.691 Å on average, respectively . In complex 6 , the P−O bond lengths are considerably shorter at 1.591(2) Å (P 1 −O 2 ) and 1.603(2) Å (P 2 −O 1 ).…”

“…The 31 P NMR spectrum of PtCl 2 ( 1 ) shows a single peak at δ 64.5 ppm, flanked by 195 Pt satellites and a coupling constant J Pt - P of 4246 Hz. This value is a clear indication of the cis coordination of the diphosphinite to the platinum center. ,,− The chemical shift difference with the uncoordinated ligand Δδ is 34.2 ppm upfield in the 31 P NMR spectrum, considerably more than that found from the reaction to yield complex 5 , where Δδ is only 5.9 ppm upfield. In the 13 C NMR spectrum, the characteristic signals for the ipso carbons of the cyclopentyl side groups appeared in the normal region, in a 1:1:1:2:2 ratio.…”

Chiral phosphites as ligands in asymmetric metal complex catalysis and synthesis of coordination compounds

“…Unusual binuclear metal complexes 120a,b containing twentyeight-membered macrocycles 193 should also be pointed out.…”