TY - JOUR

T1 - Reactions of K2[Fe3Q(CO)9] (Q = Se, Te) with AsI3

T2 - Synthesis and Structures of the First {Fe3TeAs} Clusters with Capping µ3-AsI and Bridging µ6,κ3:κ3-As2 Ligands

AU - Ilyin, Igor Yu

AU - Konchenko, Sergey N.

AU - Pushkarevsky, Nikolay A.

PY - 2015/1/1

Y1 - 2015/1/1

N2 - Reactions of cluster salts K2[Fe3Q(CO)9] (Q = Se, Te) with AsI3 in CH2Cl2 proceed differently depending on the chalcogen atom and the reaction conditions. For Te, the product of addition of μ3-AsI vertex to the initial cluster, [Fe3(CO)9(μ3-Te)(μ3-AsI)] (2b) is the main component of the solution. By action of traces of water, such as wet silica gel, 2b is converted to a dimeric cluster [{Fe3(CO)9(μ3-Te)}2(μ6,κ3:κ3-As2)] (5), whose molecules contain two identical square-pyramidal cores joined by diarsane moiety. For Se, the product 2a, analogous to 2b, was only found on the basis of mass-spectra, as main component of the reaction solution, but could not be separated because of its instability and similarity of its properties to those of [Fe3(CO)9Se2], a by-product. Two other products, [Fe3(CO)9(μ3-Se)(µ4,κ3:κ2-AsSe)Fe2(CO)6(μ-I)] (3) and K[{Fe3(CO)9(μ3-Se)(μ4-As)}2Fe(CO)3I] (4) were only found as little amount of crystals. The molecule of 3 consists of the pyramidal {Fe3SeAs} core linked by the As–Se bond to a {Fe2SeI} fragment. The cluster anion in 4 consists of two {Fe3SeAs} cores joined via the {Fe(CO)3I} unit. The products 3 and 4 presumably originate from the dissociation of the initial cluster core and their formation correlates with lower stability of Se-containing cluster 2a as compared to 2b.

AB - Reactions of cluster salts K2[Fe3Q(CO)9] (Q = Se, Te) with AsI3 in CH2Cl2 proceed differently depending on the chalcogen atom and the reaction conditions. For Te, the product of addition of μ3-AsI vertex to the initial cluster, [Fe3(CO)9(μ3-Te)(μ3-AsI)] (2b) is the main component of the solution. By action of traces of water, such as wet silica gel, 2b is converted to a dimeric cluster [{Fe3(CO)9(μ3-Te)}2(μ6,κ3:κ3-As2)] (5), whose molecules contain two identical square-pyramidal cores joined by diarsane moiety. For Se, the product 2a, analogous to 2b, was only found on the basis of mass-spectra, as main component of the reaction solution, but could not be separated because of its instability and similarity of its properties to those of [Fe3(CO)9Se2], a by-product. Two other products, [Fe3(CO)9(μ3-Se)(µ4,κ3:κ2-AsSe)Fe2(CO)6(μ-I)] (3) and K[{Fe3(CO)9(μ3-Se)(μ4-As)}2Fe(CO)3I] (4) were only found as little amount of crystals. The molecule of 3 consists of the pyramidal {Fe3SeAs} core linked by the As–Se bond to a {Fe2SeI} fragment. The cluster anion in 4 consists of two {Fe3SeAs} cores joined via the {Fe(CO)3I} unit. The products 3 and 4 presumably originate from the dissociation of the initial cluster core and their formation correlates with lower stability of Se-containing cluster 2a as compared to 2b.

KW - Arsenic

KW - Carbonyl clusters

KW - Iron

KW - Reactivity

KW - Selenium

KW - Tellurium

UR - http://www.scopus.com/inward/record.url?scp=85028131462&partnerID=8YFLogxK

U2 - 10.1007/s10876-014-0775-4

DO - 10.1007/s10876-014-0775-4

M3 - Article

AN - SCOPUS:85028131462

VL - 26

SP - 257

EP - 268

JO - Journal of Cluster Science

JF - Journal of Cluster Science

SN - 1040-7278

IS - 1

ER -