Two Routes of Electrophilic Addition and Unexpected Cluster Core Transformation in the Reactions of the K2[Fe3(μ3‐Q)(CO)9] (Q = Se, Te) Clusters with iPr2PCl

Zeitschrift fur Anorganische und Allgemeine Chemie - Tập 633 Số 13-14 - Trang 2408-2413 - 2007
Nikolay A. Pushkarevsky1, A.V. Virovets1, Stefan Gerber2, Sergey N. Konchenko1
1Novosibirsk/Russia, Nikolaev Institute of Inorganic Chemistry, Siberian Division of RAS
2Leipzig/Deutschland, Institut für Anorganische Chemie, Fakultät für Chemie und Mineralogie, Universität Leipzig

Tóm tắt

AbstractThe reactions of the K2[Fe3(μ3‐Q)(CO)9] (Q = Se (K2[1a]), Te (K2[1b])) clusters with iPr2PCl in THF lead to the formation of mixtures of two products: [{Fe2(CO)6(μ‐PiPr2)}2(μ4,η2‐Q2)] (2a, 2b) and [Fe3(μ3‐Q)(μ‐PiPr2)2(CO)7] (3a, 3b). The compounds 3a and 3b are the products of addition of two {PiPr2}+ units to two Fe‐Fe edges of the initial cluster accompanied by the elimination of two CO‐ligands. The compounds 2a and 2b are the products of the initial cluster core fragmentation followed by assembling of the diiron fragments via Q–Q bond formation.In contrast to that the reaction of K2[1a] with iPr2PCl in CH2Cl2 leads mostly to the electrophilic insertion of {PiPr2}+ into the Se–Fe bond and formation of [(μ‐H)Fe3(μ3,η2‐SePiPr2)(CO)9] (4a). Reaction of K2[1b] with iPr2PCl in CH2Cl2 leads primarily to unstable unidentified products, although 2b and 3b in minor amounts present in the reaction solution. The crystal structures of 2a, 2b, 3a and 4a were determined by single‐crystal X‐ray diffraction.

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Tài liệu tham khảo

Whitmire K. H., 1997, Adv. Organomet. Chem., 42, 145

Fenske D., 1994, Clusters and colloids: from theory to applications, 212

Gubin S. P., 1994, Koord. Khim., 20, 403

10.1016/S0277-5387(00)84930-X

10.1016/S0898-8838(08)60222-6

10.1016/S0898-8838(08)60006-9

10.1016/S0898-8838(08)60061-6

10.1021/om00004a036

10.1021/ic00105a052

10.1016/S0020-1693(99)00134-6

10.1021/ic00088a037

10.1021/om960767t

10.1016/S0022-328X(02)01659-5

10.1039/b210839a

10.1023/B:JOCL.0000005065.76523.69

10.1007/BF02494651

10.1016/0277-5387(95)00315-0

10.1016/0277-5387(96)00267-7

10.1016/S0277-5387(96)00433-0

10.1016/S0277-5387(96)00473-1

10.1016/S1387-7003(99)00142-2

Konchenko S. N., 1997, Electrochemical Soc. Proc., 865

10.1007/s10876-007-0148-3

10.1134/S1070328406060042

10.1002/cber.19851181227

10.1021/om980428v

10.1021/ic00088a037

10.1007/s11172-006-0336-6

G. M. Sheldrick SHELXS‐97 Universität Göttingen 1996.

G. M. Sheldrick SHELXL‐97 Universität Göttingen 1997.

N. A. Pushkarevsky Dissertation Nikolaev Institute of Inorganic Chemistry Novosibirsk 2004.

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Zeitschrift fur Anorganische und Allgemeine Chemie

Tập 633 Số 13-14

2408-2413

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