On the reactivity of platina‐β‐diketones: a straightforward synthesis of trans‐acetylchlorobis(phosphine)platinum(II) complexes and their reactivity

Abstract

The platina-β-diketone [Pt 2 {(COMe) 2 H} 2 (µ-Cl) 2 ] (1) was found to react with monodentate phosphines to yield acetyl(chloro)platinum(II) complexes trans-[Pt(COMe)Cl(PR 3 ) 2 ] (PR 3 = PPh 3 , 2a; P(4-FC 6 H 4 ) 3 , 2b; PMePh 2 , 2c; PMe 2 Ph, 2d; P(n-Bu) 3 , 2e; P(o-tol) 3 , 2f; P(m-tol) 3 , 2g; P(p-tol) 3 , 2h). In the reaction with P(o-tol) 3

Accessing Stable Magnesium Acyl Compounds: Reductive Cleavage of Esters by Magnesium(I) Dimers

“…Inspection of relevant metrical data for the compounds (Table ) reveals that their acyl C−O bonds (cf. 1.252(3) Å in [ t Bu 2 Al{μ‐OC( t Bu)} 2 Al t Bu 2 ]) are slightly longer than those typically seen in terminal transition metal acyls (e.g., 1.220(6) Å in [(Ph 3 P) 2 ClPt{C(O)Me}]), but significantly shorter than normal C−O single bonds (ca. 1.42 Å).…”

“…[10] In order to confirmt he proposed structures of the magnesium acyl complexes, and to shed furtherl ight on the natureo f the bonding within their acyl ligands, X-ray crystallographic studies of 1-4 were carried out. The complexes represent the first structurally authenticated s-block acyls anda ll possess similar unsymmetrical acyl and alkoxide/aryloxide bridged dimeric structures, as depicted in Figure 2f or the representative complex, 4.I nspection of relevant metrical data for the compounds ( [18] )a re slightly longer than those typicallys een in terminal transition metal acyls (e.g.,1 .220 (6) in [(Ph 3 P) 2 ClPt{C(O)Me}] [20] ), but significantly shorter than normal CÀOs ingle bonds (ca. 1.42 ).…”

Complexes trans-Pt(BODIPY)X(PEt3)2: excitation energy-dependent fluorescence and phosphorescence emissions, oxygen sensing and photocatalysis

“…2.08(1) Å for R = Ph or 2.069(8) Å for R = C 6 H 4 F-4). 39,40 With deviations of 2.8°to 6.2°for the angle P1-Pt-P2 and 1.0°to 4.2°for bond angle C1-Pt-X (X = donor atom of the anionic ligand) and a maximum deviation of 4.0°for cis-angles X-Pt-P and C1-Pt-P from the ideal values and a coplanarity of all donor atoms with the Pt(II) ion the coordination centre exhibits a close to ideal square planar coordination geometry. This is also indicated by the summations of bond angles at the Pt(II) ion, which range from 359.94°to 360.20°.…”

Reactivity of Quinoline-8-carbaldehyde toward Platina-β-diketone and Acetyl(amine)platinum(II) Complexes. Formation of Acyl(hydroxyalkyl)platinum(IV)

“…The IR spectrum shows absorptions due to terminal acyl groups and the 13 C{ 1 H} NMR spectrum shows resonances at 231.7 (d) ppm, due to the acylquinoline fragment trans to phosphorus ( 2 J P,C = 120 Hz),and at 222.8 (d) ppm, due to the acetyl group cis to phosphorus ( 2 J P,C = 8 Hz). The 31 P NMR spectrum of complex 5 contains a singlet with satellites at 28.1 ppm, and the 1 J Pt,P = 1755 Hz coupling constant agrees with a phosphorus atom trans to an acyl group. ,, The platinum chemical shift, −3630 (d) ppm, is as expected for a platinum(II) complex . Other donors such as pyridine and tetrahydrofuran are unable to cleave the acetyl bridges in 4 under the same reaction conditions.…”

“…The 31 P NMR spectrum of complex 5 contains a singlet with satellites at 28.1 ppm, and the 1 J Pt,P = 1755 Hz coupling constant agrees with a phosphorus atom trans to an acyl group. 13,26,37 The platinum chemical shift, −3630 (d) ppm, is as expected for a platinum(II) complex. 34 Other donors such as pyridine and tetrahydrofuran are unable to cleave the acetyl bridges in 4 under the same reaction conditions.…”