Insertion of CO 2 , Ketones, and Aldehydes into the C−Li Bond of 1,3,5-Triaza-7-phosphaadamantan-6-yllithium (original) (raw)
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Organometallics, 1987
The reaction of Pb(C0)3(P-t-BuzPh)3 (1) with 3 equiv of HCl at-50 O C results in immediate formation of PtHCl(CO)(P-t-Bu,Ph) (2) in which the hydride ligand is assigned to the position trans to the CO ligand. Complex 2 isomerizes rapidly at higher temperatures to give a second complex, PtHCl(CO)(P-t-BuzPh) (3), with the hydride ligand trans to the chloride ligand. Complex 3 slowly converts to a dinuclear Pt(1) complex shown by X-ray crystallography to be PtzC1z(CO)2(P-t-Bu2Ph)z (4). Complex 4 crystallizes in the monoclinic space group P2Jc with 2 = 4 in a unit cell of dimensions a = 15.418 (1) A, b = 14.751 (1) A, c = 16.051 (2) A, and p = 108.61 (1)". The structure was refined by using 4065 independent reflections with 203 variables to R1 = 0.046 and Rz = 0.053. 4 contains an unsupported Pt-Pt bond (2.628 (1) A), and the phosphine ligands are located trans to this bond. The Pt atom coordination spheres are essentially square-planar with a dihedral angle of 109.9" between the two planes. The rotational energy of the Pt-Pt bond and the relative stability of 4 and a hypothetical C1-bridged isomer are examined by using EHMO calculations. 4 also can be prepared by reacting 1.5 equiv of Clz with 1 while reaction of 1 or 4 with excess C12 gives Pt(Cl),(CO)(P-t-BuPh) (7). Addition of excess NaBH4 to a solution of 3 regenerates 1, and reaction of 3 with AgPF6 gives [ (Pt3(~-C0)3(P-t-Bu2Ph)3)zAg] [PF6] (6). Complex 6 has been spectroscopically characterized as a Ag cation sandwiched between two units of 1. 6 is also the product of the reaction of 1 and AgPF,. a Estimated standard deviations in the least significant figure(s) are given in parentheses. Anisotropically refined atoms are given in the form of the isotropic equivalent thermal parameter defined as (4/3)[a2~(1,i) + ~~(2 , 2) + c*~(3,3) + ab(cos y)~(1,2) + ac(cos B)B(1,3) + bc(cos a)B(2,3)]. cipitate was obtained by filtration; yields are quantitative; 'H
Inorganica Chimica Acta, 2018
A new one-pot synthetic procedure to new water-soluble rhenium and technetium complexes, directly from the corresponding permetallated species, is here presented. The new water-soluble M(IV) and M(III), (M = Re, Tc) paramagnetic complexes were obtained by treating [MO4]with an excess of PTA (1,3,5-triaza-7-phosphaadamantane), in water. In the presence of SnCl2, the complexes [MCl3(PTA)3]Cl, (M = Re, 1; Tc, 3), were obtained in good yield, while in the absence of SnCl2 the unexpected species containing methylated PTA, [MCl4(PTA-Me)2]Cl, (M = Re, 2; Tc, 4), were produced. A preliminary study of the reactivity of these products with N,N-diethyldithiocarbamate was also carried out: the diamagnetic binuclear μ-oxo species [M2O3(Et2NCS2)4] (M = Re, 6; Tc, 7) were isolated from the reactions of 1, 2 and 4 with dithiocarbamate. The reaction of 3 gave rise to an unusual epta-coordinated technetium(III) complex [Tc(Et2NCS2)3(PTA)] (5). The X-ray crystal structures of the new PTA complexes 2, 4, 5 and 7 have been determined.
Inorganic Chemistry, 2004
6 -C)[Pt-(PBu t 3 )], 8, and Ru 5 (CO) 12 (η 6 -C 6 H 6 )(µ 6 -C)[Pt(PBu t 3 )] 2 , 9. Compound 8 contains a Ru 5 Pt metal core in an open octahedral structure. In solution, 8 exists as a mixture of two isomers that interconvert rapidly on the NMR time scale at 20°C, ∆H q ) 7.1(1) kcal mol -1 , ∆S q ) −5.1(6) cal mol -1 K -1 , and ∆G 298 q ) 8.6(3) kcal mol -1 . Compound 9 is structurally similar to 8, but has an additional Pt(PBu t 3 ) group bridging an Ru−Ru edge of the cluster. The two Pt(PBu t 3 ) groups in 9 rapidly exchange on the NMR time scale at 70°C, ∆H q ) 9.2(3) kcal mol -1 , ∆S q ) −5(1) cal mol -1 K -1 , and ∆G 298 q ) 10.7(7) kcal mol -1 . Compound 8 reacts with hydrogen to give the dihydrido complex Ru 5 (CO) 11 (η 6 -C 6 H 6 )(µ 6 -C)[Pt(PBu t 3 )](µ-H) 2 , 10, in 59% yield. This compound consists of a closed Ru 5 Pt octahedron with two hydride ligands bridging two of the four Pt−Ru bonds. Figure 5. ORTEP diagram of the molecular structure of Ru5(CO)11-(η 6 -C6H6)(µ6-C)[Pt(PBu t 3)](µ-H)2, 10, showing 40% probability thermal ellipsoids.
Synthesis and reactivity of a heterometallic carbon dioxide complex
Inorganic Chemistry, 1990
Reduction of C 0 2 by (COD)RhH,OsP, (COD = 1,5-cyclooctadiene; P = PMe2Ph) proceeds at 1 atm and 25 "C in benzene or T H F to give H,Os(CO)P,, [(COD)Rh],0sH2C0,P3 (I), and H20. The metal-containing products are characterized by NMR and vibrational spectroscopy (including products from I3CO2), as well as an X-ray structure determination of compound I. Crystal data (-155 "C): a = 10.338 (4) A, b = 23.184 (11) A, c = 19.943 ( 8 ) A, p = 123.20 (I)", with Z = 4 in space group P2,/c. Space-filling models of I show that only the oxygens of the coordinated C 0 2 are accessible to external reagents, and Nat (as the BPhL salt) is shown to bind in T H F with a large formation constant but to exchange raidly on the N M R time scale with free I. Reaction of 1 with ZnBr, in THF also gives a 1:l adduct, which has been characterized by NMR and vibrational spectroscopy, as well as X-ray diffraction. Crystal data (at -150 "C): a = 19.677 (11) A, b = 11.267 (5) A, c = 22.376 (15) A, 6 = 103.59
Thermal and spectroscopic investigation of new binuclear Pt(II) complexes with carboxylic acids
Journal of Thermal Analysis and Calorimetry, 2009
The thermal decomposition of the binuclear Pt(II) complexes with acetate, propionate, valerate and izovalerate ligands were studied by TG and DTA techniques. The Pt(II) complex with acetic acid (PtAA) was stable up to 343.15 K, Pt(II) complex with propionic acid (PtPrA) was stable up to 323.15 K, Pt(II) complex with valeric acid (PtVA) was stable up to T=313.15 K and Pt(II) complex with isovaleric acid (PtIvA) was stable up to 408.15 K. The PtAA complex was investigated again after a year by thermogravimetric analysis. After the thermal decomposition of the Pt(II) complexes with carboxylic acids, only in the PtVA complex and PtAA complex (investigated after a year) the final residue contains only platinum, while in the rest complexes the solid residue was a mixture of platinum and platinum carbides (PtC 2 , Pt 2 C 3).
The reaction of Co4(CO)12 with Ph2PCH2CH2PPh2. Spectroscopic identification of polymeric products
Journal of Organometallic Chemistry, 1986
readily undergoes replacement of CO by l,l-bis(diphenylphosphino)ethane (DPPE) and several derivatives have been characterized. In addition to {[Co,(CO),,],(~-DPPE)} (I) and [Co,(CO),,(DPPE)] (II), two polymeric products have been identified by IR and 31P NMR spectroscopy. The 13C and 31P variable temperature NMR spectra of I and II are reported.
A series of four-coordinate air stable and water soluble cis-and trans-Pt(II) and Pd(II) complexes containing two PTA or DAPTA ligands (PTA = 1,3,5-triaza-7-phosphaadamantane; DAPTA = 3,7-diacetyl-1,3,7-triaza-5-phosphabicyclo[3.3.1]nonane) with the general formulas, [PtR 2 (PTA) 2 ], [M(Me)X(PTA) 2 ], [Pt(Et)X(PTA) 2 ], [MR 2 (DAPTA) 2 ], [MX 2 (DAPTA) 2 ], and [M(Me)X(DAPTA) 2 ] (where M = Pt or Pd; R = Me, Et, C≡CR (R = Ph, SiMe 3); X = Cl, Br, I) were prepared by ligand displacement starting from [M(R) 2 (COD)], [M(R)(X)(COD)] or precursors or metathesis reactions utilizing [MCl 2 (PR 3) 2 ] precursors in good yields (63-90%). The complexes were characterized by multinuclear NMR, IR, MS, and elemental analysis experiments and in some cases by X-ray crystallography studies. Complexes, cis-[PtMe 2 (PTA) 2 ] (cis-1), trans-[Pt(Me)Cl(PTA) 2 ] (trans-3a), trans-[PtCl 2 (PTA) 2 ] (trans-4), [trans-[Pt(C≡CPh) 2 (PTA) 2 ] (trans-6), and trans-[PtI 2 (DAPTA) 2 ] (trans-13c) were characterized by X-ray crystallography. The molecular structures reveal, in general, distorted square planar geometries at the metal center. For the DAPTA complexes, both syn-and anti-conformations of the DAPTA rings were observed depending upon the nature of the groups at the metal center.
CO2 Activation with Bulky Neutral and Cationic Phenoxyalanes
Organometallics, 2013
The sterically crowded aluminum diphenolate (2,6-Mes 2 C 6 H 3 O) 2 AlEt (2; Mes =2,4,6-Me 3 C 6 H 2 −) was converted into the ionic species [(2,6-Mes 2 C 6 H 3 O) 2 Al] + [CHB 11 Cl 11 ] − (6) by ethide abstraction with the silylium salt [Et 3 Si][CHB 11 Cl 11 ] or by a combination of β-hydride abstraction and concomitant ethylene elimination with the trityl salt [Ph 3 C][CHB 11 Cl 11 ]. Compound 6 consists of solvent-separated ions, and the cation features very short Al•••C contacts involving the flanking mesityl groups, leading to an overall distorted-tetrahedral coordination geometry around the aluminum center. Analogous reactions with the diphenolate (2,6-tBu 2-4-MeC 6 H 2 O) 2 AlEt (1) led to tert-butyl transfer to the benzene solvent to afford tert-butylbenzene as the main product. A 1:1 mixture of the triphenolate (2,6-Ph 2 C 6 H 3 O) 3 Al and tri-tert-butylphosphine forms a frustrated Lewis pair, which reacts with CO 2 at room temperature to give the compound (2,6-Ph 2 C 6 H 3 O) 3 AlOC(O)Pt-Bu 3 (8). The high Lewis acidity of 6 catalyzes the scrambling of the subsituents of Et 3 SiH at room temperature to give Et 4 Si, Et 2 SiH 2 , and EtSiH 3 and also the reduction of CO 2 to d 5-toluene (C 6 D 5 CH 3) and CH 4 at 82°C in d 6-benzene solution.