Organotin-nitrogen compounds

Much longer tin-nitrogen intramolecular distances have been observed in some internally chelated organotin derivatives of nitrogen-containing donors. It is perhaps useful at this point to cite some structures of organotin compounds containing 

Tin-nitrogen dative bonds in the range 2.511-2.56 A were measured in some internally chelated organotin derivatives containing ort/ o-dimethylaminomethylene donor groups, 112a and 112b [279, 280]. 

Trimethyltin(IV) cyanide, Me3SnCN, has a similar chain structure, 114, with trigonal bipyramidal tin and equalized Sn-C and Sn-N bond distances this leads to the interpretation that this structure is best described as an arrangement of Me3Sn+ and CN ions with the CN ordered in direction along an axis, but disordered in orientation along this axis, with perhaps a small amount of covalent 

Trimethylgermanium(IV) cyanide, MesGeCN, mentioned here for comparison, is monomeric and unassociated, because the shortest intermolecular contact between germanium and nitrogen (3.57 A) is the value expected for the van der Waals distance [284]. 

Bis(trimethyltin(IV) carbodiimide, Me3SnNCNSnMe3, forms an infinite helical network, 115, of planar SnMe3 groups linked by linear N=C=N units (Sn- - N 2.47 A) [285]. The observed tin-nitrogen distance suggests that this results from secondary-bond association between SnMe3+ groups and NCN anions. 

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Formation of Tin-Transition or Inner Transition-Metal Bond 5.8.5.4. from Organotin-Nitrogen Compounds... 

S.4.3. by Reaction of Organotin-Nitrogen Compounds with Other Complexes of the Transition or Inner Transition Metals. 

More recently, organotin azides and tin derivatives of hydrazine, 1,3-diphenyltriazene, formamide, urea, isourea, guanidine, amidine, carbo-diimide, carbamic, and thiocarbamic acids, an imidoether and imido-phosphoranes have been prepared, so that now almost every imaginable type of organotin-nitrogen compound has become known. 

Addition reactions of organotin alkoxides and distannoxanes with compounds containing multiple carbon-nitrogen bonds affording a variety of organotin-nitrogen compounds have been reported (92). The first reactions of this kind studied were additions of trialkyltin alkoxides to alkyl and aryl isocyanates, e.g.. 

Organotin nitrogen compounds are now very numerous s, and tin derivatives of amines,... 

The reader is encouraged to consult the excellent review by Veith concerning cyclic tin(II)-nitrogen compounds (107), which provides a complement to heterocycles containing organotin(IV). 

The organotin derivatives of phosphorus, arsenic, antimony, and bismuth have much in common with the corresponding derivatives of nitrogen, the most obvious difference being that the nitrogen compounds are unreactive towards oxygen, whereas the others are oxidised in air ... 

Tin-nitrogen bonded compounds are generally formed by reaction of an alkali or alkaline earth metal amide with an organotin halide compounds of the types R Sn(NR2)4 , (n = 1-3), (R3Sn) NR 3 (n = 1-3), and cyc/o-(R2SnNR ) (n = 2 or 3) can be prepared (equation 79). Other routes include transaminations (equations 80 and 81). Tin carboxamides and sulfonamides have been obtained by reaction of tin oxides or hydroxides with amides (equation 82). 

Tin-119m Mossbauer data for several classes of organotin-nitrogen bonded compounds have been reported, including iV-stannyl-amines, -imines. 

The first organogermylamines and organogermazanes were obtained around 1930 by C. A. Kraus et al. The work on the organotin chemistry of analogous compounds having tin—nitrogen bonds started even later, viz. around 1960. Today many metal-nitrogen compounds of both elements are... 

The organotin amine compounds, with a few exceptions, are liquids. They are extremely sensitive toward moisture when exposed to the air they immediately liberate amine or ammonia. Thermal stability on the other hand is good. Most compounds can be distilled without decomposition. From NMR studies it has been concluded 86) that the tin-nitrogen bond in diethylaminotin compounds is purely covalent. 

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