Stibines synthesis

MLTC bands, S, 575 NMR.5,574 Raman, 5, 575 stereochemistry, 5,538-572 stibine ligands, S, 584 sulfides, S, 584 sulfurdiimine reactivity, 2,194 sulfur dioxide, 5,584 sulfur ligands, 5,584 synthesis, 5,536-538... 

In 1996, we started more detailed investigations on group 13/15 compounds containing the heavier elements of group 15, Sb and Bi, focussing on the synthesis of aluminum and gallium stibines and bismuthines. At the same time. Wells et al. also began to prepare M—Sb adducts and heterocycles (M = B, Ga, In). These studies, which are the object of this review, resulted in... 

Detailed procedures for the synthesis of various often used [Ni°L4] complexes (L = phosphines, arsines, stibines, alkyl isocyanides) and [Ni°L 2] complexes (L = bipyridine, phenantroline, diphosphines, diarsines) have been compiled.2413... 

The number of gold complexes containing tertiary phosphines, arsines, or stibines as ligands is large because of the wide use of the fragment AuL+, mainly with L = PPh3, in the synthesis of... 

Scheme 3. Synthesis of group 13-stibine and bismuthine adducts.

Table 3 Summary of Nickel Complexes with Phosphines, Arsines and Stibines, and their Methods of Synthesis...

Although bis-2,2 -biphenylylenephenylstiborane (5-phenyl-5,5 -spirobi[5Zf-diben-zostibole]) (150) was first prepared by the tosylimine method134), it was later shown that the more traditional procedure starting from appropriate stibine dihalides 2S) was more convenient for the synthesis of such compound types13S). 

The single crystal X-ray structure of fra .y-[Ru(bipy)2(PPh3)2]2+1122,1123 and the synthesis of related bis(phosphine) complexes1005 have been reported. Reaction of [RuCljL ] (L = bipy,1124, 2-(aryl-azo)pyridine1066) with phosphine, arsine and stibine ligands (I/) affords the complexes [RuC1(L)2L ]+ while with bidentate ligands L [Ru(bipy)2L ]2+ can be isolated.1124 (See Section 45.5). 

A common method for the synthesis of tertiary stibines with alkyl, aryl, or other organic groups is the reaction between Grignard reagents and SbCls (equation 1) in diethylether or tetrahydrofiiran. 

Other methods of organoantimony hydride synthesis are reactions of R2SbLi with (Me3NH)Cl or methanolysis of silylstibines RSb(SiMc3)2 or R2SbSiMc3. Vinyl stibine H2C=C(H)-SbH2 is obtained from vinyl tributylstaimane on successive reactions (equation 8) with SbCb and BusSnH. ... 

PdL ] complexes have been prepared for a large number of phosphines (mono and bidentate), phosphites, arsines, and stibines by procedures similar to those shown for the synthesis of [Pd(PPh3)4] in Scheme 1. 

The reactivities of alkyl halides are in the sequence RI > RBr > RCl and MeX > EtX > PrX. Benzyl hahde reactions with tin do not require catalysts (equation 2). For less reactive halides, the catalysts and promoters employed include metals (sodium, magnesium, zinc, or copper), Lewis bases (amines, triorganophosphines and -stibines, alcohols, or ethers), iodides, and onium salts (R4MX). The use of tin-sodimn alloys can result in tri- or tetraorganotin products. Electrochemical synthesis has also been reported, e.g. the formation of R2SnX2 from the oxidation of anodic tin by RX in benzene solution and the formation of ILtSn from RI (R = Me or NCCH2CH2) and cathodic tin. 

The addition of methoxide or cyanide ions to cyclopropene 280 gives ° mixtures of isomeric alkenes upon methylation or protonation via allyl anions. However, triphenyl-phosphine, -arsine, or -stibine, and dimethyl sulphide afford the corresponding ylides 281. Photochromic l,8a-dihydroindolizines result from reaction of spiroannelated cyclopropenes of the type 280 with pyridines. The synthesis proceeds to ylides of the type 281 which cyclize to give the observed products. 

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