An Approach to Heterometallic Complexes with Selenolate and Tellurolate Ligands: Crystal Structures of cis-[Mn(CO)₄(SePh)₂]^-, [(CO)₃Mn(μ-SeMe)₃Mn(CO)₃]^-, (CO)₄Mn(μ-TePh)₂Co(CO)(μ-SePh)₃Mn(CO)₃, and (CO)₃Mn(μ-SePh)₃Fe(CO)₃

Abstract

Oxidative addition of diorganyl diselenides to the coordinatively unsaturated, low-valent transition-metal-carbonyl fragment [Mn(CO)(5)](-) produced cis-[Mn(CO)(4)(SeR)(2)](-). The complex cis-[PPN][Mn(CO)(4)(SePh)(2)] crystallized in triclinic space group P&onemacr; with a = 10.892(8) Å, b = 10.992(7) Å, c = 27.021(4) Å, alpha = 101.93(4) degrees, beta = 89.79(5) degrees, gamma = 116.94(5) degrees, V = 2807(3) Å(3), and Z = 2; final R = 0.085 and R(w) = 0.094. Thermolytic transformation of cis-[Mn(CO)(4)(SeMe)(2)](-) to [(CO)(3)Mn(&mgr;-SeMe)(3)Mn(CO)(3)](-) was accomplished in high yield in THF at room temperature. Crystal data for [Na-18-crown-6-ether][(CO)(3)Mn(&mgr;-SeMe)(3)Mn(CO)(3)]: trigonal space group R&thremacr;, a = 13.533(3) Å, c = 32.292(8) Å, V = 5122(2) Å(3), Z = 6, R = 0.042, R(w) = 0.041. Oxidation of Co(2+) to Co(3+) by diphenyl diselenide in the presence of chelating metallo ligands cis-[Mn(CO)(4)(SePh)(2)](-) and cis-[Mn(CO)(4)(TePh)(2)](-), followed by a bezenselenolate ligand rearranging to bridge two metals and a labile carbonyl shift from Mn to Co, led directly to [(CO)(4)Mn(&mgr;-TePh)(2)Co(CO)(&mgr;-SePh)(3)Mn(CO)(3)]. Crystal data: triclinic space group P&onemacr;, a = 11.712(3) Å, b = 12.197(3) Å, c = 15.754(3) Å, alpha = 83.56(2) degrees, beta = 76.13(2) degrees, gamma = 72.69(2) degrees, V = 2083.8(7) Å(3), Z = 2, R = 0.040, R(w) = 0.040. Addition of fac-[Fe(CO)(3)(SePh)(3)](-) to fac-[Mn(CO)(3)(CH(3)CN)(3)](+) resulted in formation of (CO)(3)Mn(&mgr;-SePh)(3)Fe(CO)(3). This neutral heterometallic complex crystallized in monoclinic space group P2(1)/n with a = 8.707(2) Å, b = 17.413(4) Å, c = 17.541(4) Å, beta = 99.72(2) degrees, V = 2621(1) Å(3), and Z = 4; final R = 0.033 and R(w) = 0.030.

Synthesis and Characterization of the Five-Coordinate Sixteen-Electron Manganese(I) Complex [Mn(CO)3(S-C6H4-NH)]-

“…Recent work in this laboratory has shown that the anionic metal carbonyl fragments ([Mn(CO) 5 ] - and [PhEFe(CO) 4 ] - (E = Se, Te)) activate the E−E bond of diorganyl dichalcogenides to yield cis -[Mn(CO) 4 (ER) 2 ] - and fac -[Fe(CO) 3 (EPh) 3 ] - complexes which are useful in the syntheses of (CO) 4 Mn(μ-ER) 2 Co(CO)(μ-ER) 3 Mn(CO) 3 with a unique terminal Co III −CO bond, [(CO) 3 M(μ-SePh) 3 M‘(μ-SePh) 3 M(CO) 3 ] -/0 (M = Mn, M‘ = Co; M = Fe, M‘ = Ni, Zn, Cd, Fe) with homoleptic hexaselenolatometal core, and distorted square planar [Ni(CO)(SPh) n (SePh) 3 - n ] - ( n = 0, 1, 2), the biomimetic nickel-site structure of [NiFeSe] hydrogenases and CO dehydrogenase. In this paper we combine the dichalcogen synthetic technology with the potential for intramolecular H-bonding to synthesize five-coordinate sixteen-electron Mn(I) complex [Mn(CO) 3 (S-C 6 H 4 -NH)] - stabilized by S,N π-donation of bidentate [S−C 6 H 4 −NH] 2- ligand.…”

Distorted Square Planar Ni(II)−Chalcogenolate Carbonyl Complexes [Ni(CO)(SPh)n(SePh)3-n]-(n= 0, 1, 2): Relevance to the Nickel Site in CO Dehydrogenases and [NiFeSe] Hydrogenase

“…Recent work in this laboratory has shown that cis -[Mn(CO) 4 (ER) 2 ] - (E = Se, Te; R = phenyl, alkyl) serve as chelating ligands and selenolate ligand-transfer reagents in the syntheses of heterometallic chalcogenolate species 12a,b and that fac -[Fe(CO) 3 (SePh) 3 ] - exhibits a unique coordination behavior toward divalent nickel ion …”

“…The sequences of reaction given in Scheme reasonably accounts for the observation. The oxidative addition of diphenyl diselenide across the Ni−Ni bond, bridge-breaking, and displacement of a coordinated C 5 H 5 - ligand by an incoming tridentate metallo ligand fac -[Fe(CO) 3 (SePh) 3 ] - must be accompanied by cyclopentadienyl ligand-transfer from Ni(II) to Fe(II), concomitant Fe(II)−SePh bond cleavage, and a labile carbonyl ligand shifting from Fe(II) to Ni(II) (CpNi(CO)(SePh), thermally unstable, converted into [CpNi(μ-SePh)] 2 at room temperature, and the addition of fac -[Fe(CO) 3 (SePh) 3 ] - to [CpNi(μ-SePh)] 2 in THF led to formation of [Ni(CO)(SePh) 3 ] - and CpFe(CO) 2 (SePh)) 12a. These results establish that the same stoichiometric quantities of CpFe(CO) 2 (SePh) are formed concurrently with [PPN][Ni(CO)(SePh) 3 ].…”

“…The [Ni II (CO)(SePh) 3 ] - exhibits a shorter Ni−CO distance (1.729(8) Å) than [Ni(NS 3 t Bu )(CO)] + (1.85(1) Å) 17 and [Ni(PS3*)(CO)] - (1.75(3) Å (PS3* = tris(3-phenyl-2-thiophenyl)phosphine)) . The terminal Fe(II)−SePh bond length of 2.413(3) Å in CpFe(CO) 2 (SePh) is shorter than the average Fe(II)−SePh bond length of 2.459(2) Å in fac -[Fe(CO) 3 (SePh) 3 ] - (Figure ) 12c 1 ORTEP drawing and labeling scheme of the [Ni(CO)(SePh) 3 ] - anion.…”

Heterotrimetallic Iron(II)−Nickel(II)−Manganese(I) Chalcogenolate Complexes Containing a Heteroleptic Hexachalcogenolatonickel(II)/Homoleptic Hexathiolatonickel(II) Core

“…Recent work in this laboratory showed that cis -[Mn(CO) 4 (ER) 2 ] - and fac -[Fe(CO) 3 (SePh) 3 ] - complexes are useful in the syntheses of heterotrimetallic Mn(I)−Co(III)−Mn(I)-chalcogenolate complexes [(CO) 4 Mn(μ-ER) 2 Co(CO)(μ-E‘R) 3 Mn(CO) 3 ] (E = E‘ = Te, R = Ph; E = Te, E‘ = Se, R = Ph; E = E‘ = Se, R = Me) with a unique Co(III)−CO bond, and [(CO) 3 M(μ-SePh) 3 M‘(μ-SePh) 3 M(CO) 3 ] -1/0 (M = Mn, M‘ = Co; M = Fe, M‘ = Fe, Cd, Zn, Ni) with a homoleptic hexaselenolatometal core. 3b, In these reactions, the complexes fac -[Fe(CO) 3 (SePh) 3 ] - and cis -[Mn(CO) 4 (ER) 2 ] - act as potential “chelating metallo ligands” and selenolate ligand-transfer reagents. 5c, …”