Assembling Ligand Substitution Reactions Monitored by VT 31P{H} NMR Spectroscopy In Order to Shine Light on the Mechanism of Formation of the Pd–Pd Bond-Containing {Pd2 (dmb)2(diphos)2+}
                n
              , {Pd2(diphos′)2 (dmb)2+}
                n
               and {Pd2 (dppm)2 (diphos)2+}
                n
               Coordination/Organometallic Polymers

Samar, Dalila; Harvey, Pierre D.

doi:10.1007/s10904-006-9079-y

J Inorg Organomet Polym

2007

DOI: 10.1007/s10904-006-9079-y

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Assembling Ligand Substitution Reactions Monitored by VT 31P{H} NMR Spectroscopy In Order to Shine Light on the Mechanism of Formation of the Pd–Pd Bond-Containing {Pd2 (dmb)2(diphos)2+} n , {Pd2(diphos′)2 (dmb)2+} n and {Pd2 (dppm)2 (diphos)2+} n Coordination/Organometallic Polymers

Dalila Samar

Pierre D. Harvey

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Cited by 5 publications

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An Original Calix[4]arene‐Containing Oligomer/Polymer Catalyst for Homogeneous Hydroformylation

Mongrain

Harvey

2008

Macromol. Rapid Commun.

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The title compound (10) was prepared from the calix[4]arene precursor (11) to form the ligand 5,11‐bis(methyl(diphenylphosphino))‐25,26,27,28‐tetra‐n‐propoxy calix[4]arene (12), which was reacted with [Rh(COD)Cl]2 (COD = 1,5‐cyclooctadienyl) and TlPF6 as chloride scavenger, in 31% overall chemical yield. The dimer structure in solution was demonstrated by the measurements of the 31P NMR spin‐lattice relaxation time (T1) in comparison with the ligand itself. Computer modeling shows that the dimer macrocycle exhibits many possible conformers, including some with obvious steric hindrance about the Rh atom, but no apparent ring stress. 10 was tested for the catalytic homogeneous hydroformylation of hex‐1‐ene and compared with other closely related analogue systems recently reported in the literature.magnified image

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An Original Calix[4]arene‐Containing Oligomer/Polymer Catalyst for Homogeneous Hydroformylation

Mongrain

Harvey

2008

Macromol. Rapid Commun.

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A Structural and Spectroscopic Investigation of Octahedral Platinum Bis(dithiolene)phosphine Complexes: Platinum Dithiolene Internal Redox Chemistry Induced by Phosphine Association

et al. 2014

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The complexes [Pt(mdt)2] (4; mdt = methyldithiolene, [Me2C2S2](n-)), [Pt(adt)2] (5; adt = p-anisyldithiolene, [(MeO-p-C6H4)2C2S2](n-)), and [Pd(adt)2] (10) have been prepared in yields of ≥90% via transmetalation reactions with the corresponding [R2Sn(S2C2R'2)] complexes (R = (n)Bu, R' = Me; R = Me, R' = -C6H4-p-OMe, 3). Intraligand C-S and C-Cchelate bond lengths (~1.71 and ~1.40 Å, respectively) obtained by X-ray crystallography show these compounds to be comprised of radical monoanions mdt(•-) and adt(•-). The six-coordinate octahedral adducts [Pt(adt)2(dppe)] [6; dppe = 1,2-bis(diphenylphosphino)ethane], trans-[Pt(adt)2(PMe3)2] (8), and trans-[Pt(mdt)2(PMe3)2] (9) have also been prepared, and crystal structures reveal dithiolene ligands that are fully reduced ene-1,2-dithiolates (C-S and C-C(chelate) = ~1.77 and 1.35 Å, respectively). Reduction of the dithiolene ligand thus occurs to accommodate the +IV oxidation state typical of octahedral six-coordinate platinum. The cyclic voltammogram of 5 shows two fully reversible reductions at -0.11 and -0.84 V in CH2Cl2 (vs Ag/AgCl), attributed to successive (adt(•-) + e(-) → adt(2-)) processes, and a reversible oxidation at +1.01 V. The cyclic voltammogram of 9 shows two reversible oxidations at +0.38 and +0.86 V, which are assigned as successive (adt(2-) → adt(•-) + e(-)) oxidations. Consistent with their formulation as having fully reduced dithiolene ligands, the UV-vis spectra for 6, 8, and 9 show no low-energy absorptions below 700 nm, and the S K-edge XAS spectra of 6 and 8 show dithiolene sulfur that is reduced relative to that in 5. The introduction of PMe3 to 10 did not produce the palladium analogue of 8 but rather [Pd(adt)(PMe3)2] (11). The reaction of [PdCl2(PPh3)2] with Li2(mdt) produced a mixture of [Pd(mdt)(PPh3)2] (12, 20%) and [(Ph3P)Pd(μ-1,2-mdt-S,S':S)2Pd(PPh3)] (13, 28%), with the latter having C2 symmetry with a Pd2S2 core structure folded along the S···S axis.

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Inorganic and organometallic polymers

Noonan

Gates

2008

Annu. Rep. Prog. Chem., Sect. A: Inorg. Chem.

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Polymers composed partially or entirely of inorganic elements in the main chain possess unique structures, properties and applications. This report summarizes the developments in the synthesis and study of macromolecules which incorporate main group and transition elements in the polymer backbone. HighlightsMajor accomplishments in the synthesis of inorganic polymers reported in 2007 include: the use of self-assembly to chemically micropattern polysiloxanes, the synthesis of p-conjugated oligomeric models for poly(phenylenedisilene), the preparation of novel polythiophenes bearing borane substituents, the isolation of cyclic ferrocenophane macromolecules, the ''living'' growth of micelles from ferrocenylsilane block copolymers, and the observation of novel electron transfer and conductive properties of zinc-porphyrin polymers.

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Assembling Ligand Substitution Reactions Monitored by VT 31P{H} NMR Spectroscopy In Order to Shine Light on the Mechanism of Formation of the Pd–Pd Bond-Containing {Pd2 (dmb)2(diphos)2+} n , {Pd2(diphos′)2 (dmb)2+} n and {Pd2 (dppm)2 (diphos)2+} n Coordination/Organometallic Polymers

Cited by 5 publications

References 36 publications

An Original Calix[4]arene‐Containing Oligomer/Polymer Catalyst for Homogeneous Hydroformylation

An Original Calix[4]arene‐Containing Oligomer/Polymer Catalyst for Homogeneous Hydroformylation

A Structural and Spectroscopic Investigation of Octahedral Platinum Bis(dithiolene)phosphine Complexes: Platinum Dithiolene Internal Redox Chemistry Induced by Phosphine Association

Inorganic and organometallic polymers

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