[Fe2(μsb‐CO)(CO)3(NO)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)]: Synthese,Kristallstruktur und Koordinationsisomerie |
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Authors: | Hans‐Christian Bttcher Harry Schmidt Sven Tobisch Christoph Wagner |
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Affiliation: | Hans‐Christian Böttcher,Harry Schmidt,Sven Tobisch,Christoph Wagner |
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Abstract: | Fe2(μsb‐CO)(CO)3(NO)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)]: Synthesis, X‐ray Crystal Structure and Isomerization NaFe2(μ‐CO)(CO)6(μ‐PtBu2)] ( 1 ) reacts with NO]BF4] at —60 °C in THF to the nitrosyl complex Fe2(CO)6(NO)(μ‐PtBu2)] ( 2 ). The subsequent reaction of 2 with phosphanes (L) under mild conditions affords the complexes Fe2(CO)5(NO)L(μ‐PtBu2)], L = PPh3, ( 3a ); η‐dppm (dppm = Ph2PCH2PPh2), ( 3b ). In this case the phosphane substitutes one carbonyl ligand at the iron tetracarbonyl fragment in 2 , which was confirmed by the X‐ray crystal structure analysis of 3a . In solution 3b loses one CO ligand very easily to give dppm as bridging ligand on the Fe‐Fe bond. The thus formed compound Fe2(CO)4(NO)(μ‐PtBu2)(μ‐dppm)] ( 4 ) occurs in solution in different solvents and over a wide temperature range as a mixture of the two isomers Fe2(μsb‐CO)(CO)3(NO)(μ‐PtBu2)(μ‐dppm)] ( 4a ) and Fe2(CO)4(μ‐NO)(μ‐PtBu2)(μ‐dppm)] ( 4b ). 4a was unambiguously characterized by single‐crystal X‐ray structure analysis while 4b was confirmed both by NMR investigations in solution as well as by means of DFT calculations. Furthermore, the spontaneous reaction of Fe2(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 5 ) with NO at —60 °C in toluene yields a complicated mixture of products containing Fe2(μ‐CO)(CO)4(μ‐H)(μ‐PtBu2)(μ‐dppm)] ( 6 ) as main product beside the isomers 4a and 4b occuring in very low yields. |
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Keywords: | Iron Carbonyl Nitrosyl Isomerization Crystal structure DFT calculations |
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