Investigations of Pyridine-2-thiol as a Ligand:  Synthesis and X-ray Structures of the Mixed Mo−Mn Dinuclear Complex CpMoMn(CO)₃(μ-CO)(μ-η²-pyS)(μ-η¹-pyS), the Electron-Deficient Trimolybdenum Cluster Cp₃Mo₃(μ-CO)₂(μ-S)(μ₃-S)(μ-η²-NC₅H₄), and the Mononuclear CpMo(CO)₂(μ-η²-pyS)

Abstract

The reaction of Mn2(CO)6(pyS)2 (1) with (CpMo(CO)3)2 (2) at 110 °C gives the heterodinuclear complex CpMoMn(CO)3(μ-CO)(μ-η2-pyS))(μ-η1-pyS) (3), the mononuclear molybdenum complex CpMo(CO)2(μ-η2-pyS) (4), and the 46-electron trimolybdenum cluster Cp3Mo3(μ-CO)2(μ-S)(μ3-S)(μ-η2-NC5H4) (5). Compound 4 could also be prepared in high yield from the reaction of 2 with pyridine-2-thiol at 110 °C. Compound 3 represents a rare example of a Mo−Mn heterodinuclear complex containing a μ-η2-pyridine-2-thiolato, a μ-η1-pyridine-2-thiolato, and a cyclopentadienyl ligand. The 46-electron compound 5 represents a unique example of a trimolybdenum compound containing three cyclopentadienyl ligands, an ortho-metalated pyridyl ligand, a capping sulfido, a bridging sulfido, and two semibridging CO ligands. Curiously, although this complex is formally electron deficient, it is unreactive toward two-electron donors. The structures of all the compounds have been unambiguously established by single-crystal X-ray crystallography.

Synthesis of Triruthenium Complexes Containing a Triply Bridging Pyridyl Ligand and Its Transformations to Face-Capping Pyridine and Perpendicularly Coordinated Pyridyl Ligands

“…Such a coordination mode is often observed in the trimetallic imidoyl complexes, but it has never been reported in a trimetallic pyridyl complex. All of the trimetallic pyridyl complexes that have ever been reported adopted a μ 2 -coordination, which acts as a 3e donor . While the pyridine ring is nearly orthogonal to the trimetallic plane in the μ-pyridyl complexes, that of 2a is tilted from the normal of the Ru 3 plane due to the π-coordination of the CN bond to Ru(1); the dihedral angle between the pyridine ring and the Ru 3 plane is estimated at ca.…”

“…This is in contrast to the extensive chemistry of arene clusters. Since Yin and Deeming synthesized the first trimetallic μ-pyridyl complex Os 3 (CO) 10 (μ-H)(μ-C 5 H 4 N) by the reaction of Os 3 (CO) 12 with pyridine, several trimetallic complexes containing a μ-pyridyl ligand have been prepared . However, whereas many μ 3 -benzyne complexes are known, coordination of a pyridyl group in a μ 3 fashion is less well known .…”

Reactions of the Tetrafluoroborate Complex [Mo2Cp2(κ2-F2BF2)(μ-PPh2)2(CO)]BF4 with Mono- and Bidentate Ligands Having E–H bonds (E = O, S, Se, N, P)

“…While the overall geometry of 6 is comparable to that of the dicarbonyl complexes 3 and those of different thiolate-bridged complexes of the type [Mo 2 Cp 2 (μ-SR) 2 (μ-X)­L 2 ] n + , the μ- S:S,N coordination mode is somewhat unusual for the Spy – anion. In fact, a search in the Cambridge Structural Database reported only 10 examples of compounds with this coordination mode which, excluding a couple of cationic polymeric silver compounds, are reduced to [Re 2 (μ-SMePy) 2 (CO) 6 ], [Et 4 N]­[Mo 2 (μ-SPy)­(CO) 9 ], [Mo 2 (μ-SPy) 2 (CO) 4 (PPh 3 ) 2 ], [Mo 3 (μ-SPy)­(μ 3 -SPy) 2 (CO) 6 ], [Ru 2 Cp 2 (μ-SPy) 2 ]­[PF 6 ] 2 , [MnMoCp­(μ-SPy)­(μ-κ 1 -SPy)­(μ-CO)­(CO) 3 ], [Ru 2 (μ-SPy) 3 (κ 2 -SPy) 2 ]­[CF 3 SO 3 ], and [Co 5 (μ 3 -S) 3 (μ-SPy) 4 (κ 2 -SPy) 3 (CO) 2 ] . The P and S atoms in 6 bridge the metal atoms asymmetrically, being closer to the MoN center, as expected from the different donor ability of the CO and N­(py) ligands.…”

Direct Conversion of a Si–C(aryl) Bond to Si–Heteroatom Bonds in the Reactions of η3-α-Silabenzyl Molybdenum and Tungsten Complexes with 2-Substituted Pyridines

“…X-ray crystal structure analysis revealed that complex 5 adopts a four-legged piano-stool geometry bearing a Mo–S–C–N four-membered ring (Figure S3 in the Supporting Information). The Mo–S (2.514(2) Å) and Mo–N (2.182(7) Å) bond distances of 5 are similar to the corresponding bond distances of the known Mo–S–C–N four-membered-ring complex CpMo­(CO) 2 {κ 2 ( S , N )-SC 5 H 4 N} (2.5227(9) and 2.183(2) Å, respectively) . Complex 6 was identified by comparing the 1 H NMR and IR spectroscopic data with those of the sample synthesized by an alternative method: i.e., the reaction of methyl­(pyridine) tungsten complex Cp*W­(CO) 2 (py)­Me with 2-aminopyridine.…”

“…The Mo−S (2.514(2) Å) and Mo−N (2.182(7) Å) bond distances of 5 are similar to the corresponding bond distances of the known Mo−S−C−N four-membered-ring complex CpMo(CO) 2 {κ 2 (S,N)-SC 5 H 4 N} (2.5227(9) and 2.183(2) Å, respectively). 12 Complex 6 was identified by comparing the 1 H NMR and IR spectroscopic data with those of the sample synthesized by an alternative method: i.e., the reaction of methyl(pyridine) tungsten complex Cp*W(CO) 2 (py)Me 13 with 2-aminopyridine. Complex 6 prepared by the latter reaction was characterized by 1 H and 13 C NMR, IR, and mass spectroscopy and elemental analysis (see the Experimental Section).…”