108148-24-9

Upstream product

• 10199-34-5 cis-dichlorobis(triphenylphosphine)platinum(II) 
• 64317-97-1 cyclenphosphorane 
• 118474-27-4 {(η2-HcyclenP)PtClPPH3}BF4 

Downstream Products

• 141292-21-9 (η2-P(N(CH2CH2)2N)2)Pt(Cl)dppm 
• 121288-55-9 (η2-P(N(CH2CH2)2N)2)PtIPPh3 
• 121288-56-0 (η2-P(N(CH2CH2)2N)2)PtBrPPh3 
• 121288-59-3 {(η2-P((N(CH2CH2)2N)2Me))Pt(Cl)PPh3}O3SCF3 
• 121288-54-8 (η2-P(N(CH2CH2)2N)2)Pt(SMe)PPh3 
• 121288-53-7 (η2-P(N(CH2CH2)2N)2)Pt{Co(CO)4}PPh3 
• 118474-27-4 {(η2-HcyclenP)PtClPPH3}BF4 
• 141292-18-4 {(P(N(CH₂)2N(CH₂)2)2)Pt((C₆H₅)2P(CH₂)2P(C₆H₅)2)}⁽¹⁺⁾*Cl^(1-)={(P(N(CH₂)2N(CH₂)2)2)Pt((C₆H₅)2P(CH₂)2P(C₆H₅)2)}Cl 
• 141319-34-8 {(P(N(CH₂)2N(CH₂)2)2)Pt((C₆H₅)2P(CH₂)2P(C₆H₅)2)}⁽¹⁺⁾*PF₆^(1-)={(P(N(CH₂)2N(CH₂)2)2)Pt((C₆H₅)2P(CH₂)2P(C₆H₅)2)}PF₆ 
• 108148-25-0 cis-((H₂cyclen)P)PtCl₂PPh₃}Cl 

Relevant academic research and scientific papers

Reactions of a Cyclenphosphoranide Platinum (II) Complex and the Pole of Highly Nucleophilic Substituents at the Axial Positions of a Trigonal Bipyramid

(η2-cyclenP)Pt(Cl)PPh3 1 exhibits a large variety of selective reactions due to the platinum metal and cyclenphosphoranide ligand, cyclenP.Moreover, the cyclenP ligand is capable of altering many of the usual reactions and/or mechanisms at square platinum (II) complexes.

Phosphoranide ligands with variable coordination modes. Synthesis, properties, and X-ray crystal structures of [(η2-HcyclenP)Pt(Cl)PPh3]BF4 and [(H2cyclenP)PtCl2PPh3]Cl

The complex (η2-cyclenP)Pt(Cl)PPh3 (1) is readily formed by the deprotonation of [(H2cyclenP)PtCl2PPh3]Cl (2) with NaOH in CH2Cl2. Both complexes contain phosphoranide (R4P:-) ligands. Complex 1 reacts with HBF4 to give the monoprotonated derivative [(η2-HcyclenP)Pt(Cl)PPh3]BF4 (3), a species in which one of the P-N bonds of the cyclenP unit is cleaved and the proton is attached to that nitrogen. Treatment of 3 with HCl in THF gives [(H2cyclenP)PtCl2PPh3]BF4 (4) (which contains a cation identical with that of 2), while treatment of 3 with NaCl in Me2SO leads to 1 and 2 via disproportionation. The X-ray crystal structures of 2 and 3 were obtained. Data for 2 indicate that the axial nitrogens are protonated and the cyclenP unit is oriented with its P-N axial bonds perpendicular to the platinum coordination plane. Data for 3 show that the HcyclenP unit is coordinated to the platinum via phosphine and amine linkages and that the phosphorus is four-coordinate. X-ray data: C26-N4P2Cl3Pt (2), orthorhombic, space group Pcab, a = 15.391 (4) A?, b = 17.021 (6) A?, c = 25.226 (14) A?, Z = 8, R = 0.087, Rw = 0.089; C26H31BN4F4P2ClPt (3), monoclinic, space group P21/c, a = 14.873 (3) A?, b = 13.021 (3) A?, c = 15.723 (3) A?, β = 106.654 (14)°, Z = 4, R = 0.044, Rw = 0.046.

Reaction of cyclenphosphorane with cis-dichlorobis(triphenylphosphine)platinum(II). Formation of bidentate and monodentate phosphoranide adducts and X-ray crystal structure of (η2-cyclenP)PtClPPh3

The reaction of cyclenphosphorane (cyclenPH) with cis-dichlorobis(triphenylphosphine)platinum(II) leads to two Pt-containing products, (η2-cyclenP)PtClPPh3 (1) and [cis-(H2cyclenP)PtCl2PPh3]Cl (2), in >95% yield each. Both 1 and 2 are stable to atmospheric oxygen; however, 2 is hygroscopic. The X-ray crystal structure of 1 was obtained and shows the four ligated atoms to Pt to all lie in the same plane as Pt; the sum of the cis angles about Pt is 359.6 (8)°. The cyclenP ligand in 1 is in an approximate trigonal-bipyramidal geometry. There is one long P-N bond (in the P-Pt-N triangle) of 1.872 (11) A? while the other three P-N bonds are between 1.68 and 1.70 A?. C26H31ClN4P2Pt is monoclinic, space group P21/n. Unit cell parameters: a = 11.562 (2) A?, b = 14.272 (2) A?, c = 15.556 (2) A?, β = 94.01 (1)°, Z = 4; R = 0.039, Rw = 0.046. By addition of HCl, 1 can be converted to 2.

PENTACOORDINATE PHOSPHORUS IN TRANSITION-METAL CHEMISTRY

The pentacoordinate phosphorus molecule, cyclenphosphorane (cyclenPH), is found to be a useful and unique ligand in transition-metal chemistry.It reacts with metal-carbonyl dimers to cleave the dimers and yield covalent phosphoranide-metal complexes and metal carbonyl anions.With cis-Cl2Pt(PPh3)2, two phosphoranide-metal complexes are formed, one ionic and the other covalent.A unique reaction occurs with ClRh(PPh3)3 where, initially, a product is obtained in which one of the P-N bonds of the cyclenP moiety is cleaved.This species undergoes a threefragment oxidative addition of CH2Cl2 to reform the pentacoordinate phosphorus and also form a novel P-N-C-Rh metallocycle.