111769-94-9Relevant articles and documents
Synthesis and Characterization of (C5H5)3M3(CO)6As and (C5H5)2M2(CO)4As2 and Derivatives of the Arsanetriyl Tetrahedrane
Ziegler, Manfred L.,Blechschmitt, Klaus,Nuber, Bernd,Zahn, Thomas
, p. 159 - 172 (2007/10/02)
The cluster compounds (C5H5)2M2(CO)4As2 (2a: M = Mo, 2b: M = W) and (C5H5)3M3(CO)6As (3a,b) have been prepared from the dinuclear complexes (C5H5)2M2(CO)6 (1) and metallic arsenic in a surprisingly simple reaction.The new compounds 3a and 3b were the only missing members in the homologous series AsnM4-n (n = 1-4).In the species 3 arsenic utilizes only three of its five valence electrons; therefore, electrophilic reactions at the arsenic atom have been found with (C5H5)Mn(CO)2THF and M(CO)5THF (M = Cr, Mo, W) yielding (C5H5)3Mo3(CO)6AsMn(C5H5)(CO)2 (9a) and (C5H5)3Mo3(CO)6AsM(CO)5 (7a-c).Compounds 3 are ideal starting materials for the synthesis of other tetrahedrane species with arsenic.So cluster building blocks can be exchanged for Fe(CO)5 with formation ofAs (10) and for Fe2(CO)9 yielding 2(μ-CO)3 (11).Compound 2a surprisingly reacts with the phosphorus ylide H2C=P(C6H5)3 with opening of the tetrahedrane framework and affording the chiral spirocluster As (12).The compounds are confirmed inter alia by X-ray structure analyses of 3a, 10, 11, and 12.In addition 2As22 (8a), the addition product of 2a and (C5H5)Mn(CO)2THF, has been prepared and characterized by means of X-ray structure analysis.
