Synthesis of the Novel Thiolato-Bridged and Oxo-Capped Trimetallic Clusters (η⁵-R‘C₅H₄)(CO)₂MFe₂(μ₃-O)- (μ-RS)(CO)₆ via Reactions of [Et₃NH][(μ-RS)(μ-CO)- Fe₂(CO)₆] with Triply Bonded Dimers [(η⁵-R‘C₅H₄)(CO)₂M]₂ (M = Mo, W) and Subsequent Treatment with Air. Crystal Structures of (η⁵-MeO₂CC₅H₄)(CO)

Abstract

The complex salts [Et3NH][(μ-RS)(μ-CO)Fe2(CO)6] (1: R = Et, t-Bu, Ph), prepared from Fe3(CO)12, RSH, and Et3N, react in situ with the triply bonded dimers [(η5-R‘C5H4)(CO)2M]2 (2: M = Mo, W; R‘ = H, MeCO, MeO2C, EtO2C) followed by treatment with air to give the series of novel clusters (η5-R‘C5H4)(CO)2MoFe2(μ3-O)(μ-RS)(CO)6 (compound, R, R‘: 3a, Et, H; 3b, t-Bu, H; 3c, Et, MeCO; 3d, t-Bu, MeO2C; 3e, Ph, MeO2C; 3f, Et, EtO2C; 3g, t-Bu, EtO2C; 3h, Ph, EtO2C) in 26−37% yields and (η5-R‘C5H4)(CO)2WFe2(μ3-O)(μ-RS)(CO)6 (compound, R, R‘: 3i, Et, MeO2C; 3j, t-Bu, MeO2C; 3k, Et, EtO2C) in 12−17% yields. Single-crystal X-ray diffraction analyses of 3d and 3k confirmed that (i) these clusters consist of the M−S (M = Mo, W) edge-opened square-pyramidal cluster skeleton MFe2SO with the M atom occupying its apical position and the Fe2OS atoms constructing its pyramid base and (ii) clusters 3d and 3k are single isomers in which the t-Bu and Et groups are bonded to the bridged S atoms by an equatorial type of bond.

Formation and Reactions of Novel Types of Bridging Sulfido Anions, (μ-RE)(μ-S-)[Fe2(CO)6]2(μ4-S) (E = S, Se): Synthesis and Structures of Double- and Triple-Butterfly Fe/E Cluster Complexes

“…In addition, it can be seen that the two substituents Me and p -MeC 6 H 4 on the subclusters are attached to S(2) and Se atoms by an equatorial bond and each of the three CO's attached to Fe atom is terminal. Therefore, this structure is consistent with its elemental and spectroscopic data and is similar to other μ 4 -S and μ 4 -Se double clusters, such as [(μ-MeS)Fe 2 (CO) 6 ] 2 (μ 4 -S), [(μ-EtS)Fe 2 (CO) 6 ] 2 (μ 4 -S),4c [(μ-EtS)Fe 2 (CO) 6 ] 2 (μ 4 -Se),5c and [(μ- p -MeC 6 H 4 Se)Fe 2 (CO) 6 ] 2 (μ 4 -Se) 1 ORTEP drawing of complex 7 .…”

“…Over the past two decades the bridging sulfido anions (μ-S - ) 2 Fe 2 (CO) 6 ( 1 ) and (μ-RS)(μ-S - )Fe 2 (CO) 6 ( 2 ), derived from reductive cleavage of the S−S bond of the Fe/S complex μ-S 2 Fe 2 (CO) 6 ( 3 ) by corresponding nucleophiles such as Et 3 BHLi, alkyllithium species RLi, and Grignard reagents RMgX, have played an important role in the development of the chemistry of butterfly Fe/S cluster complexes . In view of our current interest in the chemistry of butterfly Fe/E (E = S, Se) cluster complexes based on the complex anions [(μ-RE)(μ-CO)Fe 2 (CO) 6 ] - ( 4 , E = S, Se), we have begun an investigation of the reaction of [Et 3 NH] + salts of anions 4 with Fe/S complex 3 to see if the S−S bond of 3 could be cleaved by the nucleophiles of Fe-centered anions 4 . Interestingly, we found that this reaction indeed involves the reductive cleavage of the S−S bond of 3 , which was presumably caused by nucleophilic attack of the negatively charged Fe atom of 4 at the S atom of 3 to give intermediates m 1 ; then, m 1 might further lose their μ-CO ligands through coordination of the μ 3 -S atom to another Fe atom to give the novel bridging sulfido anions 5 , as shown in Scheme .…”

Formation and Chemical Reactivities of a New Type of Double‐Butterfly [{Fe2(μ‐CO)(CO)6}2(μ‐SZS‐μ)]2−: Synthetic and Structural Studies on Novel Linear and Macrocyclic Butterfly Fe/E (E=S, Se) Cluster Complexes

“…Formation of dianions [{Fe 2 (m-CO)(CO) 6 12 and Et 3 N in a molar ratio of 1:2:2 in THF was stirred at room temperature for approximately 0.5 h, the original green color of the solution changed to deep red. This indicated the formation of the [Et 3 NH] salts of a novel type of dianion 3.…”

“…[Fe 2 (m-S 2 )(CO) 6 ], [20] [Fe 3 (CO) 12 ], [24] HSCH 2 (CH 2 OCH 2 ) n CH 2 SH (n 1 ± 3), [25,26] Ph 2 PCl, [27] 1,3,5-Me(BrCH 2 ) 2 C 6 H 3 , [28] 1,4-(BrCH 2 )C 6 H 4 , [29] I(CH 2 ) 4 I, [30] CpFe(CO) 2 I, [31] and SeCl 2 [32] were prepared according to literature procedures. PhC(O)Cl, CS 2 , MeI, PhCH 2 Br, Et 3 N, and Br(CH 2 ) n Br (n 2 ± 4) were of commercial origin and used without further purification.…”

“…[Fe 3 (CO) 12 ], and Et 3 N in a molar ratio of 1:2:2 at room temperature. Interestingly, the in situ reactions of dianions 3 with various electrophiles affords a series of novel linear and macrocyclic butterfly Fe/E (E S, Se) cluster complexes.…”