ChemInform Abstract: (2+3)CYCLOADDITIONSRK. VON AZIDOMETALL‐KOMPLEXEN UND KRISTALLSTRUKTUR DES CYCLOADDUKTS VON DIAZIDO‐BIS‐(TRIPHENYLPHOSPHIN)‐PLAADIUM MIT BENZONITRIL

Kreutzer, P.; Weis, Ch.; Boehme, H.; Kemmerich, T.; Beck, Wolfgang; Spencer, Claude F.; Mason, R.

doi:10.1002/chin.197241438

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1998

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“…Attack of N 3 - most likely takes place at Os II −NCCH 3 , because 3 is air stable. Metal−tetrazolates form by cycloaddition either by reaction of N 3 - with metal nitriles or by reaction of nitriles with metal azides . Linkage isomerization of the resulting metal−tetrazolate is common and gives the least sterically hindered structure .…”

Section: Discussionmentioning

confidence: 99%

Reactivity of Osmium(VI) Nitrides with the Azide Ion. A New Synthetic Route to Osmium(II) Polypyridyl Complexes

1998

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There is an extensive reactivity chemistry between trans-[Os(VI)(tpy)(Cl)(2)(N)](+) (1) (tpy = 2,2':6',2"-terpyridine) and N(3)(-). Reaction of 1 with N(3)(-) in CH(2)Cl(2) or acetone occurs by electron transfer to give trans,trans-(tpy)(Cl)(2)Os(II)(N(2))Os(II)(Cl)(2)(tpy). In CH(3)CN, trans-Os(II)(tpy)(Cl)(2)(N(2)) forms but undergoes solvolysis to give trans-Os(II)(tpy)(Cl)(2)(CH(3)CN). 1 reacts with excess N(3)(-) in CH(3)CN to give Os(III)(tpy)(Cl)(2)(5-CH(3)-tetrazolate), which has been characterized by X-ray crystallography. This is the first known Os-tetrazolato complex. 1 reacts with N(3)(-) in the presence of CS(2) to give trans-[Os(II)(tpy)(Cl)(2)(NS)](+), SCN(-), and N(2).

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Section: Discussionmentioning

confidence: 99%