Mixed-Valence Manganese Carbonyl Complexes with Supersilyl Thiolate Ligands: [(OC)₄Mn(μ-SSitBu₃)₂Mn(THF)X] (X = Br, SSitBu₃) and Na(THF)₆[(OC)₃Mn(μ-SSitBu₃)₃MnSSitBu₃]

Abstract

The manganese carbonyl thiolates [(OC) 4 Mn(µ-SSitBu 3 ) 2 Na(THF) 2 ], [(OC) 4 Mn(µ-SSitBu 3 ) 2 Mn-(THF)Br], [(OC) 4 Mn(µ-SSitBu 3 ) 2 Mn(THF)SSitBu 3 ], and Na(THF) 6 [(OC) 3 Mn(µ-SSitBu 3 ) 3 MnSSitBu 3 ] can be prepared from the precursors Na(THF) 2 SSitBu 3 and [Mn(CO) 5 Br]. When [Mn(CO) 5 Br] is treated with 1 or 2 equiv of Na(THF) 2 SSitBu 3 , the 1:2 substitution product [(OC) 4 Mn(µ-SSitBu 3 ) 2 Na(THF) 2 ] (monoclinic, P2 1 /c) is formed quickly. When additional amounts of [Mn(CO) 5 Br] are present (as in the 1:1 reaction) or are subsequently added to the reaction mixture, the dinuclear Mn(I)Mn(II) complex [(OC) 4 Mn(µ-SSitBu 3 ) 2 Mn(THF)Br] (monoclinic, P2 1 /n) can be obtained along with [Mn 2 (CO) 10 ]. Treatment of [(OC) 4 Mn(µ-SSitBu 3 ) 2 Mn(THF)Br] with 1 equiv of Na(THF) 2 SSitBu 3 gives the mixedvalence dinuclear manganese thiolate complex [(OC) 4 Mn(µ-SSitBu 3 ) 2 Mn(THF)SSitBu 3 ] (monoclinic, C2/ c). Cocrystals of the Mn(I)Mn(II) species Na(THF) 6 [(OC) 3 Mn(µ-SSitBu 3 ) 3 MnSSitBu 3 ] with the trisulfane tBu 3 Si-SSS-SitBu 3 (trigonal, R3 j ) are obtained by the reaction of [Mn(CO) 5 Br] with 2 equiv of Na(THF) 2 SSitBu 3 . The complex anion [(OC) 3 Mn(µ-SSitBu 3 ) 3 MnSSitBu 3 ]contains a terminal thiolate ligand with a linear Mn-S-Si unit.

Structure and reactivity studies of transition metals ligated by tBuSi3X (X = O, NH, N, S, and CC)

“…The scope of this process has not been evaluated, and there is reason to believe that the ''hubcap'' motif is not simply a random byproduct. 73 Although these laboratories have ceased-for the time being-exploration of the chalcogenide-and pnictogen-based ligands, others, principally Lerner, have picked up the theme, and future elaboration of ( t Bu 3 Si) 2 P-74 and t Bu 3 SiEcontaining (E = S, 75 Se, Te) 76 organometallic and coordination compounds appears promising.…”

Synthesis, Reactivity, and Properties of N-Fused Porphyrin Manganese(I) Tricarbonyl Complexes

“…In the 13 C NMR spectrum, the signals due to three CO ligands were distinctly observed at 214.08, 216.33, and 216.82 ppm. The strong absorption bands due to the CO stretching were clearly observed at 1902, 1920, and 2005 cm –1 in the IR spectrum …”

Redetermination of (acetonitrile-κN)dicarbonyl(η5-cyclopentadienyl)iron(II) tetrafluoridoborate

“…For background to this work, see: Kü ckmann et al (2005Kü ckmann et al ( , 2007Kü ckmann et al ( , 2008Kü ckmann et al ( , 2010; Lerner (2005); Sä nger et al (2012). For a previous (incomplete) structure determination of the title compound, see: Fadel et al (1979).…”