Syntheses from Metal Vapors

S.2.2.2. Dimers and Clusters with Nonbridging Ligands 8.2.2.2.I. Syntheses from Metal Vapors. 

The nature of the complexes, synthesized from metal vapor and t-BuC=P, is highly dependent upon the nature of the metal. Thus, with iron, chromium, or vanadium atoms, pentaphosphametallocenes are obtained.51 In contrast, the phosphaalkyne and molybdenum or tungsten atoms afford homoleptic tris[i74-l,3-diphosphete] metal(O) complexes [M(tj4-P2C2- -Bu2)3] (M = Mo, W).51... 

Cobalt-arene complexes can also be synthesized from metal vapor reactions. For example, ( -C6H5Me)Co(C6F5)2 is made at low temperature and low pressure conditions (equation 55). 

It is in the synthesis of organometallic complexes that the metal-atom technique shows its greatest utility. From metal vapors, many complexes may be synthesized on a macroscale that are difficult, if not impossible, to prepare by standard, wet-chemical techniques (64, 65). In this section, we shall illustrate the vast potential that the method has in this area, although, to be sure, it is evident throughout this entire review. 

The synthetic potential of transition metal atoms in organometallic chemistry was first demonstrated by the formation of dibenzenechrom-ium (127). Apart from chromium, Ti, V, Nb, Mo, W, Mn, and Fe atoms each form well-defined complexes with arenes on condensation at low temperatures. Interaction has also been observed between arenes and the vapors of Co, Ni, and some lanthanides. Most important, the synthesis of metal-arene complexes from metal vapors has been successful with a wide range of substituted benzenes, providing routes to many compounds inaccessible by conventional reductive preparations of metal-arene compounds. 

Co-condensation of Hf and Zr atoms from an electron-gun evaporation device, with P(Me)3 and arenes at 77K gave good yields of the species [M(arene)2P(Me3)]. Metal vapor synthesis led to Fe(i7 -arene)L2 and Fe(i7 -arene)-(i7 -diene), where L is a phosphorus ligand. In addition, complexes of stoichiometry Fe(T) -diene)L3 (where L is again a... 

Dihydro-lH-l,5,2-azasilaboroles derive from the 2,5-dihydro-lH-l,2-aza-boroles ( 6.5.3.3) by substitution of the carbon neighboring N by a silicon atom. They may act as four-electron donors using electron density from the C=C double bond and the N atom. The B atom behaves as an acceptor center. Two pathways are known for complex synthesis reaction with a generated transition-metal complex fragment and reaction with metal atoms by the metal-vapor synthesis method. 

The thermal stability of alkali-metal borides is relatively low, which is expected from the high vapor pressures of the corresponding metals at high T. Consequently, the alkali-metal vapor pressure is an important parameter, and synthesis of alkali-metal boride is carried out in isothermal reactors that permit maximum alkali-metal pressure and hence optimum preparation conditions. 

The (C Me ) Sm(THF) metal vapor product provided the first opportunity ta see if Smdl) complexes (y =3.5—3.8 Ufi) could be characterized by H NMR spectroscopy (24). Fortunately, the paramagnetism doesn t cause large shifting and broadening of the resonances and hence samarium provides the only Ln(III)/Ln(II) couple in which both partners are NMR accessible. Once the existence and identity of (C Mej- SmdHF) was known, a solution synthesis was developed from KC Me and Sml THF) (44). This system is the preferred preparative route and also provides another soluble organosamarium(II) complex, [(C Me )Sm(THF)2(u-I)]2, under appropriate conditions. This is another xample of how solution studies subsequently catch up to the research targets often identified first in metal vapor reactions. 

After the activation period, the reactor temperature was decreased to 453 K, synthesis gas (H2 CO = 2 1) was introduced to the reactor, and the pressure was increased to 2.03 MPa (20.7 atm). The reactor temperature was increased to 493 K at a rate of 1 K/min, and the space velocity was maintained at 5 SL/h/gcat. The reaction products were continuously removed from the vapor space of the reactor and passed through two traps, a warm trap maintained at 373 K and a cold trap held at 273 K. The uncondensed vapor stream was reduced to atmospheric pressure through a letdown valve. The gas flow was measured using a wet test meter and analyzed by an online GC. The accumulated reactor liquid products were removed every 24 h by passing through a 2 pm sintered metal filter located below the liquid level in the CSTR. The conversions of CO and H2 were obtained by gas chromatography (GC) analysis (micro-GC equipped with thermal conductivity detectors) of the reactor exit gas mixture. The reaction products were collected in three traps maintained at different temperatures a hot trap (200°C), a warm trap (100°C), and a cold trap (0°C). The products were separated into different fractions (rewax, wax, oil, and aqueous) for quantification. However, the oil and wax fractions were mixed prior to GC analysis. 

The synthesis of chalcogenides such as those of the rare earth elements has traditionally been performed through the reaction of rare earth metals or oxides with a molten or vaporous chalcogen source in a high-temperature environment. Soft synthetic methods utilizing lower temperature conditions, such as hydrothermal or flux syntheses, can allow access also to thermodynamically metastable phases. Flux syntheses of R chalcogenides via an alkali poly-chalcogenide flux have been shown to be extremely versatile for the preparation of many new structures, some of which cannot be obtained by direct synthesis from the elements. 

Synthesis from Citronellol. Citronellol is hydrated to 3,7-dimethyloctan-l,7-diol, for example, by reaction with 60% sulfuric acid. The diol is dehydrogenated catalytically in the vapor phase at low pressure to highly pure hydroxydihydrocitronellal in excellent yield. The process is carried out in the presence of, for example, a copper-zinc catalyst [68] at atmospheric pressure noble metal catalysts can also be used [69]. 

Re arene complexes also result from application of the MVS technique to the extremely refractory Re metal (see Metal Vapor Synthesis of Transition Metal... 

The metal vapor technique, in which a metal is vaporized from a resistively heated tungsten container under high vacuum and is cocondensed with a potential ligand at -125 to -196°C, had proven useful in the synthesis of a variety of unusual low-valent transition metal complexes (67-71). With lanthanide metals, this method not only has generated low oxidation state species, but it has also provided the opportunity to study zero-valent lanthanide chemistry on an atomic/molecular basis for the first time. These studies have been important in identifying new directions in organolanthanide chemistry. 

Well-defined arene complexes of Group 4 metals in various oxidation states have been isolated. The air- and moisture-sensitive complexes Ti(r -arene)2 (56) have a sandwich structure similar to that of the related chromium compounds [176-178]. They have been used for deoxygenation of propylene oxide and coupling reaction of organic carbonyl compounds [179]. The first synthesis of 56 was cocondensation of metal vapor with arene matrix [176]. Two more convenient methods are reduction of TiCl4 with K[BEt3H] in arene solvent [180] and reaction of TiCl4(THF)2 with arene anions followed by treatment with iodine [170,176]. The latter method involves the formation of an anionic titanate complex, [Ti(ri -arene)2] (57), which can also be formed from KH and 56 [181]. 

Alternatively, Mo(r -arene)2 complexes (arene = C HjCH, C HsF, C HjCl, C6H5(NMc2), CfjH5COOMe) have been prepared by metal atom vapor synthesis from molybdenum metal and arene [50,51]. 

Figure 12.4 Evaporation-condensation generator for the synthesis of ultrafine metal particles. The cylindrical glass chamber was 0.34 m in diameter and 0.45 m in height. Metal vapor from the alumina crucible mixes with the inert gas. The vapor nucleates particles grow by condensation and deposit on the cooled copper plate by thcrmophorcsis. (After Granqvisi and Buhrman. 1976.)...

In another example, nanodustered Pt(0) catalysts based on cross-linked macro-molecular matrixes were evaluated in the hydrogenation of an a,(i-unsaturated aldehyde, citral. The monometallic catalysts exhibit remarkable selectivity for gera-niol/nerol when 2-3 nm, regularly shaped, spherical metal nanoclusters are deposited on the supports from solutions of solvated platinum atoms prepared by metal vapor synthesis (MVS). The immobilization in the polymer framework of ions of a second metal such as Fe(II), Co(II), or Zn(II) enhances the selectivity of the Pt catalysts by up to more than 90% [18],... 

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