Reactivity of platinum alkyne complexes towards N-fluorobenzenesulfonimide: formation of platinum compounds bearing a β-fluorovinyl ligand

Abstract

The platinum(0) alkyne complexes [Pt(L)(η(2)-PhC[triple bond, length as m-dash]CPh)] 1-4 were synthesized by reactions of [Pt(cod)2] with diphenylacetylene and a phosphine ligand precursor (1: L = dcpe, 2: L = xantphos, 3: L = κ(2)-(P,N)-iPr2PC3H6NMe2, 4: L = κ(2)-(P,N)-iPr2PC2H4NMe2). Treatment of 1 or 4 with NFSI gave the complexes [Pt(F){N(SO2Ph)2}(dcpe)] (5) and [Pt(PhC[double bond, length as m-dash]CFPh){N(SO2Ph)2}{κ(2)-(P,N)-iPr2PC2H4NMe2}] (8), whereas the reactivity of 2 and 3 towards NFSI led to product mixtures. The compounds [Pt(F){N(SO2Ph)2}(xantphos)] (6a) as well as [Pt(PhC[double bond, length as m-dash]CFPh){N(SO2Ph)2}{κ(2)-(P,N)-iPr2PC2H4NMe2}] (7a) and [Pt(PhC[double bond, length as m-dash]CFPh)(F){κ(2)-(P,N)-iPr2PC2H4NMe2}] (7b) were clearly identified. Ligand exchange reactions at 8 resulted in the formation of the β-fluorovinyl platinum(ii) complexes [Pt(PhC[double bond, length as m-dash]CFPh){OC(O)CF3}{κ(2)-(P,N)-iPr2PC2H4NMe2}] (9), [Pt(PhC[double bond, length as m-dash]CFPh)(FHF){κ(2)-(P,N)-iPr2PC2H4NMe2}] (10) and [Pt(PhC[double bond, length as m-dash]CFPh)(F){κ(2)-(P,N)-iPr2PC2H4NMe2}] (11). Treatment of 8 with dihydrogen yielded the fluorinated olefin (Z)-(1-fluoroethene-1,2-diyl)dibenzene and [Pt{N(SO2Ph)2}(H){κ(2)-(P,N)-iPr2PC2H4NMe2}] (12).

The Versatile Behavior of Platinum Alkyne Complexes towards XeF2: Formation of Fluorovinyl and Fluorido Complexes

“…[71] The NMR data of compound 3 are comparable to those of compound 4.T he 31 P{ 1 H} NMR spectrum of compound 3 shows ad oublet at d = 6.6 ppm with 195 Pt satellites ( 2 J(P,F trans ) = 179, 1 J(Pt,P) = 4369 Hz). [71] The NMR data of compound 3 are comparable to those of compound 4.T he 31 P{ 1 H} NMR spectrum of compound 3 shows ad oublet at d = 6.6 ppm with 195 Pt satellites ( 2 J(P,F trans ) = 179, 1 J(Pt,P) = 4369 Hz).…”

“…[71] The NMR data of compound 3 are comparable to those of compound 4.T he 31 P{ 1 H} NMR spectrum of compound 3 shows ad oublet at d = 6.6 ppm with 195 Pt satellites ( 2 J(P,F trans ) = 179, 1 J(Pt,P) = 4369 Hz). [71] The liquid injection field desorption/ionization mass spectrometry (LIFDI-MS) data revealapeak at m/z 614, which can be assigned to the [M] + ion. [71] The liquid injection field desorption/ionization mass spectrometry (LIFDI-MS) data revealapeak at m/z 614, which can be assigned to the [M] + ion.…”

“…The structure reveals as quare-planar arrangemento ft he chelating ligand and the vinyl and fluorido ligandsa tt he platinum center. [71] The F1-Pt1-C12 angle of 87.01(7)8 in compound 3 is slightly smaller than the analogousa ngle in [Pt(PhC=CFPh)(FHF){k 2 -(P,N)-iPr 2 PC 2 H 4 NMe 2 }] (F-Pt-C = 89.23(6)8). [71,87,88] The Pt1ÀC12 as well as the Pt1ÀF1 bond lengths of 2.024(2) and 2.0736 (14) ,r espectively,a re comparable with the PtÀCa nd PtÀFb ond lengths in [Pt(PhC=CFPh)(FHF){k 2 -(P,N)-iPr 2 PC 2 H 4 NMe 2 }] [PtÀC: 2.0185 (19), PtÀF: 2.0948 (11) ].…”

“…The metal-bound fluorido ligand gives rise to ad oublet of quartetsa td = À229.4 ppm with 195 Pt satellites ( 2 J(P,F trans ) = 157, 3 J(F,F) = 7, 1 J(Pt,F) = 165 Hz). [71] Additional information was provided by the 19 F, 13 CHMBC spectrum.F or compound 13 a ad oubleto fd oublets corresponding to the a-vinyl carbona tom appears at d = 104 ppm in the 13 14)s how ad ifferent reactivity towards the electrophilicf luorinating agent N-fluorbenzensulfonimid( NFSI). Note that neither for complex 7 nor for compound 8 aC ÀCc oupling reactionb yr eductivee limination of af luorinated olefine was observed in the presence of tolane,a lthough this might be thermodynamically feasible.…”

“…[55,66] Lynam and co-workersdescribed recently the formation of fluorinated alkenyla nd alkyl ligands at ruthenium centers by an outer-sphere electrophilic reaction pathway. [71] Note that in literature b-fluorovinyl goldc omplexes are discussed to be intermediates in the catalytic fluorination of symmetric and asymmetrical internal alkynest ogive fluorinated olefins. [71] Note that in literature b-fluorovinyl goldc omplexes are discussed to be intermediates in the catalytic fluorination of symmetric and asymmetrical internal alkynest ogive fluorinated olefins.…”