Heat complex

When pungent-warm herbs and bitter-cold herbs are combined, the cold and heat complex, which knots up the Qi and causes obstruction, is dissipated. 

Quinazoline derivatives may also be obtained by heating complex diazonium salts with nitriles45 under these conditions the nitrilium salt (49) first formed accepts a second nitrile molecule and the resulting product is cyclized by electrophilic attack on the ortho position of the... 

An important property of metal-bound phosphole ligands is their ability to undergo additional reactions not possible in the noncomplexed form. This is nicely illustrated by the thermally induced reactions of the palladium(ll) complex of 1-phenyl-3,4-dimethylphosphole 341 <1996IC1486>. Heating complex 341 at 145 °C in solution or at 140 °C in the solid state led to the formation of a mixed 7-phosphanorbornene-phosphole complex 343 (Scheme 114). These intramolecular [4-1-2] cycloaddition reactions are believed to proceed via the initial formation of a diallyl 1,4-biradical TS 342. Further examples of this type of reaction may be found in Section 3.15.12.1.1. 

The reaction of 1,2,3-triphenylcyclopropenylium tetraduoroborate (28) with sodium pentacar-bonylrhenium afforded the cycloprop-2-enyl-rhenium complex 39. Upon ultraviolet irradiation or heating, complex 39 split off one carbonyl ligand to give the rhenacyclobutadiene complex 40, which was in equilibrium with the )7 -cyclopropenyl-rhenium rr-complex 41. The structure of 40 was determined by X-ray crystallography. ... 

T24.3 Recall from Section 24.9(a) that heating complex oxides under stream of ammonia can lead to the partial reduction of metal oxide. It can also lead to the nitridation of the oxide forming oxide-nitrides and eventually, with high excesses of ammonia, nitrides. In this case, partial nitridation occurs ... 

Structure of (153) confirms the presence of linear hydrogen-bonded chains mediated through the N-atoms of DABCO. Upon heating, complex (153) loses DABCO and reverts to (151) in quantitative yields. Grinding (151) and DABCO in ratios other than a 1 1 stoichiometry leads to mixtures of (153) with excess, unreacted reagent. 

When heated, complexes (98) undergo a rearrangement with the formation of a new C—C bond to give the dimeric 5-substituted-4-oxa-3-bora-l,l-bihomoadamantanes (99) (Scheme 36). Dimers (99) form colorless crystals, stable in the air <8lJOM(2i9)30l>. 

Figure 6. Time dependence of the benzylidene content by heating complexes 4 (RuCl2(=CHPh)(PCy3)2. ( )), 5 (R = Cy, R = (S)-CHMePh, ( )), and 6 (R = Cy, (A)), at 85 °C in the presence of ethyl 2-brdmo-2-methylpropanoate.

Heating complex 57 at 50°C in CH3CN resulted in rapid and clean C-F bond-forming reductive elimination to afford 60 (Eq. 45). The addition of pyridine trapped the Pd-containing product as the cationic bis-pyridine adduct 61 (Eq. 45). 

Cis and trans isomers of 32 are intercontertible through the action of light and heat. Complex 32 reacts with ketones R2C=0 (R = Me, Ph) to form the seven-membened ring products 33. ... 

Heating complex 84 yields a dinuclear complex with bridging hydride and ethylidene ligands (158, Scheme 27) 158 is obtained also by reaction of ethylene with the dinuclear trihydride complex 159, which accompanies catalytic conversion of ethylene into 2-butenyl trifluoroacetate. 

Finally, a quite new series of comb polymers has been reported (Fig. 7.33) that are both mesomorphic (biphenyl aryl ester side chains) and, after doping, electrically conductive (conjugated main chain). The polymers are made by heating complexes formed between the corresponding nitrile (R—CN) and a transition-metal halide, and the process can be carried out at a mesophase temperature to allow ordered polymerization. The relationships between micro- and/or macroscopic ordering and electrical conductivity have yet to be established, but fascinating thermoelectrical applications can be envisaged. 

It is also worth to cite a set of complexes of dissymmetrical, hypervalent phosphorus-substituted methanediide for which a dilithiated form has not been isolated to date, but which present interesting structures and reactivity. Complex [8QN (AlMe2)2l was obtained by stepwise reaction of diphenyl(N-tert-butyl)iminopho-sphorano-(8-quinolyl)methane with 1 equiv. of trimethylaluminum in toluene at 60°C and subsequent reaction of a second equivalent of trimethylaluminum at 120°C [104]. When 2 equiv. of trimethylaluminum is directly added and heated, complex [AI3] is formed, for which the quinolyl substituent was methylated in positimi 2. A catalytic role of excess trialkylaluminum was highlighted (Chart 5). 

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