Dinuclear Pt(II) and Pd(I) Complexes with Bridging PPh2 Ligands from the Reaction of PPh2H with Zero-Valent Complexes of These Metals

Abstract

Reactions of PPh2H with [M(PCy3)2] (M = Pt, Pd) produce the dinuclear complexes with bridging PPh2 ligands of these metals, [{Pt(H)(PCy3)}2(μ-PPh2)2] and [{Pd(PCy3)}2(μ-PPh2)2], respectively.

Reactions of 9-Triptyceneselenol with Palladium(0) Complexes: Unexpected Formations of the Dinuclear Palladium(I) Complex [{Pd(PPh3)}2(μ-SeTrip)2] and Five-Membered Selenapalladacycle [Pd(η2(C,Se)-Trip)(dppe)]

“…The X-ray crystallographic analysis of 2 revealed that the palladium metal exhibited a trigonal-planar coordination. The Pd1-Pd1* distance (2.5821(6) Å) is comparable to those observed in the phosphido-bridged dinuclear Pd(I) complexes [{Pd(PMe 3 )} 2 (µ-P t Bu 2 ) 2 ] (2.571(2) Å) 7 and [{Pd(PCy 3 )} 2 (µ-PPh 2 ) 2 ] (2.5755(7) Å) 8 4)-96.90(4)°). 10,11 We next attempted to synthesize the Pd(II) hydrido selenolato complex using a chelating phosphine ligand such as dppe.…”

“…The X-ray crystallographic analysis of 2 revealed that the palladium metal exhibited a trigonal-planar coordination. The Pd1−Pd1* distance (2.5821(6) Å) is comparable to those observed in the phosphido-bridged dinuclear Pd(I) complexes [{Pd(PMe 3 )} 2 (μ-P t Bu 2 ) 2 ] (2.571(2) Å) and [{Pd(PCy 3 )} 2 (μ-PPh 2 ) 2 ] (2.5755(7) Å) but significantly shorter than those in the silyl-bridged dinuclear Pd(I) complexes [{Pd(PMe 3 )} 2 (μ-SiHPh 2 ) 2 ] (2.691(1) Å) and [{Pd(PEt 3 )} 2 (μ-SiHPh 2 ) 2 ] (2.699(2) Å) . Both of the Pd1−Se1 distances (2.4513(6) and 2.4693(6) Å) are close to those in the observed selenolato-bridged dinuclear Pd(II) complexes [Pd 2 (SeTh) 4 (PPh 3 ) 2 ] (Th = 2-thienyl) (2.463(1), 2.4461(1) Å) and [Pd 2 (SePh) 4 (PPh 3 ) 2 ] (2.4661(11), 2.4657(12) Å) .…”

Multimetallic Complexes Featuring a Bridging N-heterocyclic Phosphido/Phosphenium Ligand: Synthesis, Structure, and Theoretical Investigation

“…The distances between the central NHP phosphorus atoms and each Pd center are quite similar (Pd1–P2, 2.3026(9) Å; Pd1–P5, 2.2933(8) Å; Pd2–P2, 2.2816(8) Å; Pd2–P5, 2.3023(8) Å), and are substantially longer than the P (NHP) -Pd multiple bond distance in the NHP + phosphenium bridged dimer complex 3 [(PPP)Pd] 2 [PF 6 ] 2 (2.1242(16) Å) . The P (NHP) -Pd distances in 5 are, however, comparable with the P–Pd distances in reported bis(phosphide)-bridged Pd(I) dimers (2.23–2.33 Å), − suggesting that the bridging NHP ligand in complex 5 is best described as an NHP – phosphido bridging ligand. The tetrahedral geometry of the central NHP phosphorus atoms and Pd centers, as well as the bent angle between the N–P–N plane and each P–Pd bond vector (average 145.6°) are consistent with the assignment as a μ-NHP – phosphido Pd(I) dimer complex.…”

Dinuclear Palladium and Platinum Complexes with Bridging Silylene Ligands. Preparation Using (Aminosilyl)boronic Ester as the Ligand Precursor and Their Reactions with Alkynes

“…IR absorption spectra were recorded on a Shimadzu FT/IR-8100 spectrometer. Et 2 NSiPh 2 BOCMe 2 CMe 2 O, Pd(PCy 3 ) 2 , Pt(PCy 3 ) 2 , and Pt(SiHPh 2 ) 2 (PMe 3 ) 2 were prepared according to the reported procedure. HCCPh, PhCCPh, HCCC 6 H 4 Me-4, and HCCCOOMe were purchased from Tokyo Chemical Industry and distilled prior to use.…”

“…IR absorption spectra were recorded on a Shimadzu FT/IR-8100 spectrometer. Et 2 NSiPh 2 À BOCMe 2 CMe 2 À O, 10 Pd(PCy 3 ) 2 , 31 Pt-(PCy 3 ) 2 , 32 and Pt(SiHPh 2 ) 2 (PMe 3 ) 2 33 were prepared according to the reported procedure. HCtCPh, PhCtCPh, HCtCC 6 H 4 Me-4, and (d, 36H, PCH 3 , 2 J PÀH = 6.4 Hz, 3 J PtÀH = 18 Hz), 7.18 (t, 4H, C 6 H 5 para, 3 J HÀH = 7.5 Hz), 7.33 (t, 8H, C 6 H 5 meta, 3 J HÀH = 7.5 Hz), 8.23 (d, 8H, C 6 H 5 ortho, 3 J HÀH = 7.5 Hz).…”