Methane complexes

Figure 3.19 Synthesis and reactions of palladium(I) bis(diphenylphosphino)methane complexes.

The first copper(I) complex of tris(hydroxymethyl)phosphine ((760) tetrahedral) has been reported by Samuelson and co-workers. This group addressed the question of anion-controlled nuclearity and metal-metal distances in copper(I)-bis(diphenylphosphino)methane complexes, and in this endeavor they reported the structures of complexes (761) (Cu-Cu separation 3.005-3.128 A), (762) (Cu-Cu separation 3.165 A) and (763) (tetrahedral Cu-Cu 3.293 A). 6 They synthesized and provided structural evidence of oxy anion- encapsulated copper(I) complexes of this ligand. The complexes (764) (distorted tetrahedral Cu-Cu 3.143 A), (765) (distorted tetrahedral Cu-Cu 3.424A), (766) (distorted trigonal Cu-Cu 3.170A), and (767) (Cu-Cu 3.032-3.077A) were reported. They studied solid-state emission spectra of these complexes.567 During this pursuit they... 

Thus, with the exception of the weak neutral methane complex, it appears that the ratio AEna52f AEm increases with H-bond strength, and the relative importance of Aiw(2) tends to be higher in ionic than in neutral complexes. 

Solution Studies of Tris(pyrazolyl)methane Complexes. 118... 

Although the poly(pyrazolyl)borate complexes of iron(II) have been well known for many years, [1] it is only recently that the complexes with the tris(l-pyrazolylmethane ligand, HC(pz)3, [45-48] have been studied in detail. It should be noted that poly(pyrazolyl)methane ligands, such as the tris(l-pyrazolylmethane ligand, are neutral, whereas the poly(pyrazolyl)bo-rate ligands, such as the tris(l-pyrazolyl)borate ligand, HB(pz)3", are monoanions. As a consequence, the metal(II) poly(pyrazolyl)methane complexes are dications and often have quite different properties from those of the analogous metal(II) poly(pyrazolyl)borate molecular complexes. But, in spite of these differences there are often very close structural similarities between the dicationic complexes and the neutral complexes. Therefore the study of the pyrazolylmethane complexes will parallel that of the borate complexes discussed above. 

The complex TpPtMeH2 was synthesized by reacting TpPtMe(CO) with water (66). While it is stable towards reductive elimination of methane at 55 °C, deuterium incorporation from methanol-c/4 solvent occurs rapidly into the hydride positions and subsequently, more slowly, into the methyl position (Scheme 15). The scrambling into the methyl position has been attributed to reversible formation of a methane complex which does not lose methane under the reaction conditions (75,76). Similar scrambling reactions have been observed for other metal alkyl hydrides at temperatures below those where alkane reductive elimination becomes dominant (77-84). This includes examples of scrambling without methane loss at elevated temperature (78). 

Protonation reactions of the related dimethyl(hydrido)platinum(IV) complex TpMe2PtMe2H (58) leading to rapid methane reductive elimination have also been reported (86). This protonation was shown to occur exclusively at the pyrazole nitrogen, presumably forming a five-coordinate Pt(IV) intermediate. This species should undergo C-H coupling, and while a Pt(II) methane complex is not observed, trapping with... 

The observation of stable Pt(IV) alkyl hydrides upon protonation of Pt(II) alkyls has provided support for the idea that the methane which had been observed in earlier studies (89-92) of protonation of Pt(II) methyls could be produced via a reductive elimination reaction from Pt(IV). An extensive study of protonation of Pt(II) methyl complexes was carried out in 1996 (56) and an excellent summary of these results appeared in a recent review article (14). Strong evidence was presented to support the involvement of both Pt(IV) methyl hydrides and Pt(II) cr-methane complexes as intermediates in the rapid protonolysis reactions of Pt(II) methyls to generate methane. The principle of microscopic... 

The question of which pathway is preferred was very recently addressed for several diimine-chelated platinum complexes (93). It was convincingly shown for dimethyl complexes chelated by a variety of diimines that the metal is the kinetic site of protonation. In the system under investigation, acetonitrile was used as the trapping ligand L (see Fig. 1) which reacted with the methane complex B to form the elimination product C and also reacted with the five-coordinate alkyl hydride species D to form the stable six-coordinate complex E (93). An increase in the concentration of acetonitrile led to increased yields of the methyl (hydrido)platinum(IV) complex E relative to the platinum(II) product C. It was concluded that the equilibration between the species D and B and the irreversible and associative1 reactions of these species with acetonitrile occur at comparable rates such that the kinetic product of the protonation is more efficiently trapped at higher acetonitrile concentrations. Thus, in these systems protonation occurs preferentially at platinum and, by the principle of microscopic reversibility, this indicates that C-H activation with these systems occurs preferentially via oxidative addition (93). 

Fig. 4. Relevant structures for the discussion of methane activation by (bipyrimi-dine)PtCl2 Methane complex of Pt(II) (A) methyl(hydrido)platinum(IV) complex, the product of the oxidative addition (B) transition state for intramolecular deprotonation of the methane complex ( cr-bond metathesis , sometimes also called electrophilic , C) intermolecular deprotonation of the methane complex ( electrophilic pathway , D).

In a study of the methane complex [(diimine)Pt(CH3)(CH4)]+ (diimine = HN=C(H)-C(H)=NH), relevant to the diimine system experimentally investigated by Tilset et al. (28), theoretical calculations indicate preference for the oxidative addition pathway (30). When one water molecule was included in these calculations, the preference for oxidative addition increased due to the stabilization of Pt(IV) by coordinated water (30). The same preference for oxidative addition was previously calculated for the ethylenediamine (en) system [(en)Pt(CH3)(CH4)]+ (151). This model is relevant for the experimentally investigated tmeda system [(tmeda)Pt(CH3)(solv)]+ discussed above (Scheme 7, B) (27,152). For the bis-formate complex Pt(02CH)2, a a-bond metathesis was assumed and the energies of intermediates and transition states were calculated... 

The meta-selectivity for toluene activation, observed for both systems, is very unusual (Fig. 5). Also remarkable is the switch in selectivity from aryl C-H activation to benzylic activation inp-xylene, just by changing the chelate ligand from the diimine equipped with trifluoromethyl substitutents in the meta-positions of the phenyl residue to the diimine bearing methyl substituents in the ortho-positions (Fig. 5). The authors suggested that the C-H bond activation is reversible and the isomeric a-methane complexes are in equilibrium prior to the substitution of... 

A. Borysow and L. Frommhold. Collision induced rototranslational absorption spectra of binary methane complexes (CH4-CH4). J. Molec. Spectrosc., 123 293, 1987. 

In nonpolar solvents such as CH2C12 the bridging carbonyl (X) is formed preferentially. It has a remarkably low carbonyl stretching frequency of 1638 cm-1 and an X-ray structure determination of the corresponding bis(diphenylarsino)methane complex shows that there is no Pt-Pt bond (3,9,10). The complex therefore is considered as a dimetal-lated formaldehyde derivative. 

FIGURE 13. Dependence of the computed (529Si chemical shifs on the Si-C distance in the H3Si+-methane complex (27) data at IGLO/BII//MP2(fc)/6-31G versus TMS. Reproduced by permission of Wiley-VCH from Reference 6... 

A series of complexes (Chart 5) have been reported that comprise both a poly(pyrazolyl)borate ligand and an intramolecularly chelating, monoanionic coligand. These are typically obtained via halide displacement and dimer cleavage by the respective sodium or potassium poly(pyrazo-lyl)borate salt, a means by which 462—466,45 467—469,143 and 470 479144 145 were each prepared in good yield, while the related poly (pyrazolyl)methane complexes 480+— 483+ were isolated as their perchlorate salts in the presence of NaClO 145... 

Finally in this section, the platinum complex BpP rihr -CgH OMe) (186) and related bis(pyrazolyl)methane complex salts [(H2Cpz2)M(r 1 r 2-CgHi2OMe)]PF6 (M = Pd 189.PF6, Pt 190.PF6) have been obtained from [M (ri1 ri2-C8FIi2OMe)Cl]2 and NaBp, or H2Cpz2/NFl4PF6, respectively (Scheme 15, Section III.B.l).73 The palladium analogue of 186 has proven inaccessible. These complexes all exhibit fluxionality, ascribed to inversion of the EN2M boat (E = B, C). 

Natural waters Co-precipitation with Fe(OH)3 selective separation by precipitation determined as dibenzoyl methane complex Laser fluorometry 5 ppb No data Eral 1989 > > r < H O... 

Cyclization of N-trichloroacetamides using copper(I)-bis[(45)-(l-methylethyl)oxazolin-2-yl]methane complex afforded the corresponding y-lactams in high yield (85-95%) but low diastereoselectivity (6%) (eq 10). ... 

The complexes cis-(CO)3LMH [M = Mn or Re, L = diphos or bis(diphenylphos-phino)methane] react readily with CS2 at RT . The diphos complexes yield simple monodentate dithioformate products. In the bis(diphenylphosphino)methane complexes, one of the ligand phosphorus atoms attacks the carbon atom of the dithioformate, forming a quaternery zwitterion (cf. the Pd complex helow). 

Several new complexes of iminophosphoranes have been reported by Cavell and co-workers (Scheme 9). Reaction of dimethyl zinc with bis- trimethylsilyl-imino-diphenylphosphorano methane (61) yields zinc complex (62) via elimination of methane. Complex (62) did not react with adamantyl nitrile or isonitrile but does undergo nucleophilic addition reactions with hetereroallenes such as carbodiimides and isocyanates. Thus, treatment of (62) with adamantyl isocyanate produces the novel tripodal alkyl zinc complex (63). Iminophos-phorane (61) reacts with [Sm(NCy2)3(THF)] and tetrakis(benzyl)zirconium(IV)... 

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