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Title: Synthesis of chiral heterobimetallic tris(phosphinoamide) Zr/Co complexes

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Journal Article: Publisher's Accepted Manuscript
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Journal Volume: 114; Journal Issue: C; Related Information: CHORUS Timestamp: 2017-10-03 21:48:51; Journal ID: ISSN 0277-5387
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United Kingdom

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Saper, Noam I., Bezpalko, Mark W., Foxman, Bruce M., and Thomas, Christine M. Synthesis of chiral heterobimetallic tris(phosphinoamide) Zr/Co complexes. United Kingdom: N. p., 2016. Web. doi:10.1016/j.poly.2015.11.001.
Saper, Noam I., Bezpalko, Mark W., Foxman, Bruce M., & Thomas, Christine M. Synthesis of chiral heterobimetallic tris(phosphinoamide) Zr/Co complexes. United Kingdom. doi:10.1016/j.poly.2015.11.001.
Saper, Noam I., Bezpalko, Mark W., Foxman, Bruce M., and Thomas, Christine M. 2016. "Synthesis of chiral heterobimetallic tris(phosphinoamide) Zr/Co complexes". United Kingdom. doi:10.1016/j.poly.2015.11.001.
title = {Synthesis of chiral heterobimetallic tris(phosphinoamide) Zr/Co complexes},
author = {Saper, Noam I. and Bezpalko, Mark W. and Foxman, Bruce M. and Thomas, Christine M.},
abstractNote = {},
doi = {10.1016/j.poly.2015.11.001},
journal = {Polyhedron},
number = C,
volume = 114,
place = {United Kingdom},
year = 2016,
month = 8

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Publisher's Version of Record at 10.1016/j.poly.2015.11.001

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  • The palladium-catalyzed coupling reactions of {eta}{sup 5}-iodocyclopentadienyl complexes of Fe, W, Mn, and Re with Bu{sub 3}SnC{triple bond}CH yield the corresponding {eta}{sup 5}-ethynylcyclopentadienyl derivatives ({eta}{sup 5}-HC{triple bond}CC{sub 5}H{sub 4})ML{sub n} (M = Fe, W, Mn, Re). Upon reaction with Et{sub 2}NSnR{sub 3} (R = Me, Bu), the acetylenic proton is replaced with a trialkyltin group, forming the {eta}{sup 5}((trialkylstannyl)ethynyl)cyclopentadienyl derivatives ({eta}{sup 5}-R{sub 3}SnC{triple bond}CC{sub 5}H{sub 4})ML{sub n}. A second palladium-catalyzed coupling reaction between these trialkyltin derivatives and ({eta}{sup 5}-iodocyclopentadienyl)metal complexes affords the heterobimetallic complexes L{sub n}M({eta}{sup 5}-C{sub 5}H{sub 4})C{triple bond}C({eta}{sup 5}-C{sub 5}H{sub 4})M{prime}L{sub m} (M and M{prime} = Fe, W,more » Mo, Mn, Re). The crystal structure of Ph{sub 3}P(CO){sub 2}Mn({eta}{sup 5}-C{sub 5}H{sub 4})C{triple bond}C({eta}{sup 5}-C{sub 5}H{sub 4})W(CO){sub 3}CH{sub 3} confirmed the general structure of these heterobimetallic complexes.« less
  • The reduction chemistry of heterobimetallic dihydrides are of much interest. Three heterobimetallic monohydride complexes containing Rh bound to either Re or Ta were isolated during synthetic attempts at preparing heterobimetallic dihydrides. The mode of synthesis, characterization, and reactivity of these three heterobimetallic compounds are discussed herein. 19 refs.
  • As starting materials for heterobimetallic complexes, [RuCp(PPh{sub 3})CO(PPh{sub 2}H)]PF{sub 6} and [RuCp(PPh{sub 3})CO({eta}-dppm)]-PF{sub 6} were prepared from RuCp(PPh{sub 3})(CO)Cl. In the course of preparing [RuCp({eta}{sup 2}-dppm)({eta}-dppm)]Cl from RuCp(Ph{sub 3}P)({eta}-dppm)Cl, the monomer RuCpCl({eta}-dppm){sub 2} was isolated. The uncommon coordination mode of the two monodentatebis(phosphines) was confirmed by X-ray crystallography [a = 11.490(1) {angstrom}, b = 14.869(2) {angstrom}, c = 15.447(2) {angstrom}, {alpha} = 84.63(1){degrees}, {beta} = 70.55(1){degrees}, {gamma} = 72.92(1){degrees}, V = 2378.7(5) {angstrom}{sup 3}, d{sub calc} = 1.355 g cm{sup -3} (298 K), triclinic, P1, Z = 2]. The dppm-bridged bimetallic complexes RuCp(PPh{sub 3})Cl({mu}-dppm)PtCl{sub 2}, RuCpCl({mu}-dppm){sub 2}PtCl{sub 2}, and [RuCp(PPh{submore » 3})CO({mu}-dppm)PtCl{sub 2}]PF{sub 6} each exhibit electrochemistry consistent with varying degrees of metal-metal interaction. The cationic heterobimetallic complexes [Mo(CO){sub 3}({mu}-dppm){sub 2}Pt(H)]PF{sub 6} and [MoCp-(CO){sub 2}-({mu}-PPh{sub 2})({mu}-H)Pt(PPh{sub 3})(MeCN)]PF{sub 6} were prepared by chloride abstraction from the corresponding neutral bimetallic species and show electrochemical behavior similar to the analogous Ru/Pt complexes.« less
  • A series of actinide-transition metal heterobimetallics has been prepared, featuring thorium, uranium and cobalt. Complexes incorporating the binucleating ligand N[-(NHCH2PiPr2)C6H4]3 and Th(IV) (4) or U(IV) (5) with a carbonyl bridged [Co(CO)4]- unit were synthesized from the corresponding actinide chlorides (Th: 2; U: 3) and Na[Co(CO)4]. Irradiation of the isocarbonyls with ultraviolet light resulted in the formation of new species containing actinide-metal bonds in good yields (Th: 6; U: 7); this photolysis method provides a new approach to a relatively rare class of complexes. Characterization by single-crystal X-ray diffraction revealed that elimination of the bridging carbonyl is accompanied by coordination ofmore » a phosphine arm from the N4P3 ligand to the cobalt center. Additionally, actinide-cobalt bonds of 3.0771(5) and 3.0319(7) for the thorium and uranium complexes, respectively, were observed. The solution state behavior of the thorium complexes was evaluated using 1H, 1H-1H COSY, 31P and variable-temperature NMR spectroscopy. IR, UV-Vis/NIR, and variable-temperature magnetic susceptibility measurements are also reported.« less
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