Manganese Carbonyl Complexes Research Articles

The Diversity of Difluoroacetylene Coordination Modes Obtained by Coupling Fluorocarbyne Ligands on Binuclear Manganese Carbonyl Sites

Recent work has shown that the fluorocarbyne ligand CF, isoelectronic with the NO ligand, can be generated by the defluorination of CF(3) metal complexes, as illustrated by the 2006 synthesis by Hughes et al. of [C(5)H(5)Mo(CF)(CO)(2)] in good yield by the defluorination of [C(5)H(5)Mo(CF(3))(CO)(3)]. The fluorocarbyne ligand has now been investigated as a ligand in the manganese carbonyl complexes [Mn(CF)(CO)(n)] (n = 3, 4) and [Mn(2)(CF)(2)(CO)(n)] (n = 4-7) by using density functional theory. In mononuclear complexes, such as [Mn(CF)(CO)(4)], the CF ligand behaves very much like the NO ligand in terms of pi-acceptor strength. However, in the binuclear complexes the two CF ligands couple in many of the low-energy structures to form a bridging C(2)F(2) ligand derived, at least formally, from difluoroacetylene, FC[triple bond]CF. The geometries of such [Mn(2)(C(2)F(2))(CO)(n)] complexes suggest several different bonding modes of the bridging C(2)F(2) unit. These include bonding through the orthogonal pi bonds of FC[triple bond]CF, similar to the well-known [R(2)C(2)Co(2)(CO)(6)] complexes, or bonding of the C(2)F(2) unit as a symmetrical or unsymmetrical biscarbene. This research suggests that fluorocarbyne metal chemistry can serve as a means for obtaining a variety of difluoroacetylene metal complexes, thereby avoiding the need for synthesizing and handling the very unstable difluoroacetylene.

Reactions of rhenium and manganese carbonyl complexes with 1,8-bis(diphenylphosphino)naphthalene: Ligand chelation, C–H and C–P bond-cleavage reactions

Reaction of [Re 2(CO) 8(MeCN) 2] with 1,8-bis(diphenylphosphino)naphthalene (dppn) afforded three mono-rhenium complexes fac-[Re(CO) 3(κ 1:η 1-PPh 2C 10H 6)(PPh 2H)] ( 1), fac-[Re(CO) 3{κ 1:κ 1:η 1-(O)PPh 2C 10H 6(O)PPh(C 6H 4)}] ( 2) and fac-[ReCl(CO) 3(κ 2-PPh 2C 10H 6PPh 2)] ( 3). Compounds 1– 3 are formed by Re–Re bond cleavage and P–C and C–H bond activation of the dppn ligand. Each of these three complexes have three CO groups arranged in facial fashion. Compound 1 contains a chelating cyclometalated diphenylnaphthylphosphine ligand and a terminally coordinated PPh 2H ligand. Compound 2 consists of an orthometalated dppn-dioxide ligand coordinated in a κ 1:κ 1:η 1-fashion via both the oxygen atoms and ortho-carbon atom of one of the phenyl rings. Compound 3 consists of an unchanged chelating dppn ligand and a terminal Cl ligand. Treatment of [Mn 2(CO) 8(MeCN) 2] with a slight excess of dppn in refluxing toluene at 72 °C, gave the previously reported [Mn 2(CO) 8(μ-PPh 2) 2] ( 4), formed by cleavage of C–P bonds, and the new compound fac-[MnCl(CO) 3(κ 2-PPh 2C 10H 6PPh 2)] ( 5), which has an unaltered chelating dppn and a terminal Cl ligand. In sharp contrast, reaction of [Mn 2(CO) 8(MeCN) 2] with slight excess of dppn at room temperature yielded the dimanganese [Mn 2(CO) 9{κ 1-PPh 2(C 10H 7)}] ( 6) in which the diphenylnaphthylphosphine ligand, formed by facile cleavage of one of the P–C bonds, is axially coordinated to one Mn atom. Compound 6 was also obtained from the reaction of [Mn 2(CO) 9(MeCN)] with dppn at room temperature. The XRD structures of complexes 1– 3, 5, 6 are reported.

Carbonyl complexes of manganese, rhenium and molybdenum with 2-pyridylimino acid ligands

[MBr(CO) 3{ κ 2(N,O)-pyca}] [M = Mn( 1a), Re( 1b), pyca = pyridine-2-carboxaldehyde] and [MoCl(η 3-C 3H 4Me-2)(CO) 2{ κ 2(N,O)-pyca}] ( 1c) react with aminoacid β-alanine to give the corresponding iminopyridine complexes 2a– 2c. The same method affords the iminopyridine derivatives from γ-aminobutyric acid (GABA) ( 3a– 3c) and 3-aminobenzoic acid ( 4a– 4c). For complexes 2a– 2c, 3a, 3c and 4a, the solid state structures have been determined by X-ray crystallography, revealing interesting differences in their hydrogen-bonding patterns in solid state.

A manganese carbonyl complex derived from the P,N-bonding ligand (2-aminophenyl)diphenylphosphine

Thermal reaction of [H 3Mn 3(CO) 12] with Ph 2PC 6H 4NH 2-2 gives good yields of [Mn 2(CO) 6(PPh 2C 6H 4NH) 2], an X-ray single crystal structure determination of which reveals a P,N-chelating ligand with each of the NH groups, formed by deprotonation of the amine groups, bridging the two metal atoms.

Carbonyl complexes of manganese, rhenium and molybdenum with ethynyliminopyridine ligands

[MBr(CO) 5] reacts with m-ethynylphenylamine and pyridine-2-carboxaldehyde in refluxing tetrahydrofuran to give, fac-[MBr(CO) 3(py-2-CH N-C 6H 4- m-(C CH))] (M = Mn, 1a; Re, 2a). The same method affords the tetracarbonyl [Mo(CO) 4{py-2-CH N-C 6H 4- m-(C CH)}] ( 3a) starting from [Mo(CO) 4(piperidine) 2]; and the methallyl complex [MoCl(η 3-C 3H 4Me-2)(CO) 2{py-2-CH N-C 6H 4- m-(C CH)}] ( 4a) from [MoCl(η 3-C 3H 4Me-2)(CO) 2(NCMe) 2]. The use of p-ethynylphenylamine gives the corresponding derivatives ( 1b, 2b, 3b, and 4b) with the ethynyl substituent in the para-position at the phenyl ring of the iminopyridine. All complexes have been isolated as crystalline solids and characterized by analytical and spectroscopic methods. X-ray determinations, carried out on crystals of 1a, 1b, 2a, 2b, 3b, 4a, and 4b, reveals the same structural type for all compounds with small variations due mainly to the different size of the metal atoms. The reaction of complexes 1a or 2a with dicobalt octacarbonyl affords the tetrahedrane complexes [MBr(CO) 3{py-2-CH N-C 6H 4- m-{(μ-C CH)Co 2(CO) 6}}] (M = Mn, 5; Re, 6), the structures of which have been confirmed by an X-ray determination on a crystal of compound 5.

Chalcogen‐Containing Manganese Carbonyl Clusters: Synthesis and Structural Transformations

AbstractFor Abstract see ChemInform Abstract in Full Text.

Rh4(CO)12-Catalyzed Hydroformylation of Cyclopentene Promoted with HMn(CO)5. Another Example of Rh4(CO)12/HMn(CO)5 Bimetallic Catalytic Binuclear Elimination

A detailed in situ high-pressure FTIR spectroscopic study was performed to investigate the bimetallic origins of catalytic synergism in homogeneous catalysis. The reaction chosen was the homogeneous catalyzed hydroformylation of cyclopentene to cyclopentanecarboxaldehyde, starting with unmodified rhodium and manganese carbonyls as catalyst precursors in n-hexane as solvent. The spectra were analyzed by an advanced signal processing and statistical technique. Only four organometallic spectra could be found. These were RCORh(CO)4, Rh4(CO)12, HMn(CO)5, and Mn2(CO)10. A very significant increase in aldehyde formation was observed in the experiments when both rhodium carbonyl and manganese carbonyl complexes were used simultaneously. The kinetics of product formation shows a distinct linear−bilinear form in observable organometallics; k1[RCORh(CO)4][H2][CO]-1 + k2[RCORh(CO)4][HMn(CO)5][CO]-1.6. The determined activation parameters for the bilinear term were ΔH⧧ = 47 ± 8 kJ/mol and ΔS⧧ = −88 ± 28 J/(mol K). The...

New X-ray powder diffraction data for the series CpMn(CO)3, Cp(CO)2Mn=C=CHPh, [Cp(CO)2Mn]2(μ-C=CHPh), and [Cp(CO)2Mn]2(μ-C4Ph2) complexes (Cp=η5-C5H5)

Four manganese carbonyl complexes: CpMn(CO)3 (1) and its phenylvinylidene derivatives Cp(CO)2Mn=C=CHPh (2), [Cp(CO)2Mn]2(μ-C=CHPh) (3), and Cp(CO)2Mn=C=C(Ph)–C(Ph)=C=Mn(CO)2Cp (4) have been studied by X-ray powder diffraction and their unit cell parameters are reported. The monoclinic cell parameters found for complex (1) are a=12.0479(7) Å, b=7.0614(5) Å, c=10.9172(6) Å, β=117.626(2)°, Z=4, space group P2(1)/a (No. 14). The orthorhombic cells parameters for complex (2) are a=10.5240(12) Å, b=33.1105(48) Å, c=7.5007(9) Å, Z=8, space group PCCN (No. 56); for complex (3) are a=15.3545(17) Å, b=15.3966(18) Å, c=8.0033(7) Å, Z=4, space group P21212121 (No. 19). The parameters found for complexes (1–3) are in good agreement with those obtained from single crystal X-ray diffractometry. The single crystal structure of complex (4) has not been studied. The orthorhombic cell parameters for complex (4) found by X-ray powder diffraction method are a=10.0986(9) Å, b=33.2937(27) Å, c=7.4139(5) Å, Z=4, space group P21 (No. 4).

Chalcogen-Containing Manganese Carbonyl Clusters: Synthesis and Structural Transformations

Recently, we have developed several synthetic routes to the new classes of chalcogen-containing manganese carbonyl clusters, and the interesting structural transformations and reactivity of the resultant clusters have been investigated as well. In this short review, the syntheses and bonding modes of the sulfur, selenium, and tellurium-containing manganese carbonyl complexes reported by our laboratory will be presented, and the cluster growth and transformation will be systematically compared and discussed.

Synthesis and properties of oligomers of iron–manganese carbonyl complexes with bridging disulfido ligands

The reactions of activated CpFeMn(CO) 7 1a and Cp*FeMn(CO) 7 1b, Cp=C 5Me 5 with thiirane yielded the new dimeric mixed metal disulfido complexes: [CpFeMn(CO) 5(μ 3-S 2)] 2 ( 2) and [Cp*FeMn(CO) 5(μ 3-S 2)] 2 ( 3). Compounds 2 and 3 both contain two triply bridging disulfido ligands. When heated at 40 °C, compound 2 was transformed into a trimeric compound Cp 3Fe 3Mn 3(CO) 15(μ 3-S 2)(μ 4-S 2) 2, 4. Compound 4 contains three disulfido ligands, each of which has a different bridging coordination mode in the six atom metal cluster. There are three inequivalent CpFe(CO) 2 groupings linked to a central Mn 3(S 2) 3 core by the disulfido ligands. In solution, compound 4 exhibits a dynamical intramolecular exchange process that interconverts two of the three CpFe(CO) 2 groups on the NMR timescale.

Synthesis, Structure and Reactivity of [1, 2‐Bis(diphenylphosphinite)ethane]bromotricarbonylmanganese(I) with Reactions of Phosphites, Phosphonites. and Phosphinites

AbstractThe manganese carbonyl complex [MnBr(CO)3L] (1), where L = Ph2POCH2CH2OPPh2, was prepared by reacting [MnBr(CO)5] with the bidentate ligand 1, 2‐Bis(diphenylphosphinite)ethane. From this compound and the appropriate phosphite, phosphinite or phosphonite ligands were synthesized the complexes [MnBr(CO)2LL′], where L′ = P(OMe)3 (2) or P(OEt)3 (3) and [MnBr(CO)3L′2], where L′ =PPh(OEt)2 (4) or PPh2(OEt) (5).The obtained compounds have been characterized by elemental analysis, mass spectrometry, IR and NMR (1H, 13C and 31P) spectroscopies and X‐ray diffractometry for the complexes 1, 4 and 5.

Structurally adaptive multitopic ligands containing tris(pyrazolyl)methane units as supramolecular synthons: manganese carbonyl complexes

The compounds { p-C 6H 4[CH 2OCH 2C(pz) 3] 2[Mn(CO) 3] 2}(BF 4) 2 ( 1, pz=pyrazolyl ring), { p-C 6H 4[CH 2OCH 2C(pz) 3] 2[Mn(CO) 3] 2}(OTf) 2 ( 2, OTf −=CF 3SO 3 −), { m-C 6H 4[CH 2OCH 2C(pz) 3] 2[Mn(CO) 3] 2}(BF 4) 2 ( 3) and { 1,2,4,5-C 6H 2[CH 2OCH 2C(pz) 3] 4[Mn(CO) 3] 4}(BF 4) 4 ( 4) have been prepared by reaction of the respective ligands with ‘Mn(CO) 5 +’, prepared ‘in situ’ from the reaction of Mn(CO) 5Br and AgBF 4 or AgOTf in refluxing acetone. In the structures of all four complexes, the environment around the manganese atom is a slightly distorted octahedron, with the distortion caused by the restricted bite angle of the κ 3-bonded tris(pyrazolyl)methane ligand. The structurally adaptive ligands in all four complexes support extended three-dimensional (3D) supramolecular structures. An important organizational feature for the three BF 4 − complexes is a double π–π and CH⋯π interaction involving the pyrazolyl rings. The double π–π/CH⋯π interaction is intermolecular in 1 and 3 leading to the formation of chains and sheets. In the case of the tetratopic ligand in complex 4, the π–π/CH⋯π interaction is intramolecular between adjacent ( ortho) side arms. These supramolecular structures are also supported by weak CH⋯F hydrogen bonds. For 3, classic π–π interactions of the central arene rings are also involved in organizing the 3D network. For 2, the structure is organized solely by CH⋯O hydrogen bonding.

A simple route to thiacrowns. Catalytic macrocyclization of thiirane by cationic manganese carbonyl complexes

Thiirane is transformed catalytically into the symmetric thiacrowns: 1,4,7,10-tetrathiacyclododecane, 12S4; 1,4,7,10,13-pentathiacyclopentadecane, 15S5; and 1,4,7,10,13,16-hexathiacyclooctadecane, 18S6, when treated with the manganese carbonyl monocations: [Mn(CO) 4(L)(NCMe)] +, L=CO, PPh 3, PMe 2Ph and PEt 3 at room temperature. 12S4 is the major thiacrown product. Considerable amounts of polymer are also formed. The phosphine-substituted catalysts are considerably more active and give better yields of the thiacrowns than the parent carbonyl, but they also give more polymer side product.

Synthesis and characterization of manganese complexes of the dibenzophospholyl ligand

Manganese carbonyl complexes bearing dibenzophospholyl (DBP) and 1-phenyldibenzophosphole (Ph-DBP) ligands have been prepared. Reaction of Li-DBP with Mn(CO)5Br gave (µ2-DBP)(µ2-Br)Mn2(CO)8, while reaction of bis(1,1'-dibenzophospholyl) and Mn2(CO)10 yielded (µ2-DBP)2Mn2(CO)8. The phosphine adducts (Ph-DBP)Mn2(CO)9 and (Ph-DBP)2Mn2(CO)8 were obtained by reaction of Ph-DBP and Mn2(CO)10. The ligands are σ-bonded through the phosphorus atom in all complexes. The compounds were characterized by 1H, 13C, and 31P NMR and IR spectroscopy, mass spectrometry, and X-ray diffraction.Key words: dibenzophospholyl, dibenzophosphole, manganese, heterocycle.

Syntheses, reactivity, and pi-donating ligand metathesis reaction of five-coordinate sixteen-electron manganese(I) complexes: crystal structures of [Mn(CO(3)(-TeC(6)H(4)-o-NH-)](-), [(Mn(CO)(3))2(mu-SC(6)H(4)-o-S--S--C(6)H(4)-o-mu-S--)], [(CO)(3)Mn(mu-SC(6)H(4)-o-NH(2)-)]2, and [(CO)(3)Mn(mu-SC(8)N(2)H(4)-o-S-)](2)(2-).

The preparation of the varieties of five-coordinate sixteen-electron manganese(I) complexes [Mn(CO)(3)(-EC(6)H(4)-o-E'-)](-) (E = Te, Se, S, O; E' = NH, S, O) by (a) oxidative addition of 2-aminophenyl dichalcogenides to anionic manganese(0)-carbonyl, (b) pi-donating ligand metathesis reaction of complex [Mn(CO)(3)(-TeC(6)H(4)-o-NH-)](-), and (c) reduction /deprotonation of the neutral dimetallic [(Mn(CO)(3))(2)(mu-SC(6)H(4)-o-S-S-C(6)H(4)-o-mu-S-)]/[(CO)(3)Mn(mu-SC(6)H(4)-o-NH(2)-)](2) proved successful approaches in this direction. The IR nu(CO) data of the coordinatively and electronically unsaturated [Mn(CO)(3)(-EC(6)H(4)-o-E'-)](-) (E = Te, Se, S, O; E' = NH, S, O) complexes suggest the relative order of pi-donating ability of the series of bidentate ligands being [TeC(6)H(4)-o-NH](2)(-) > [SeC(6)H(4)-o-NH](2)(-) > [SC(6)H(4)-o-NH](2)(-) > [SC(6)H(4)-o-S](2)(-) > [SC(6)H(4)-o-O](2)(-) > [OC(6)H(4)-o-O](2)(-). Proton NMR spectra of the [Mn(CO)(3)(-EC(6)H(4)-o-NH-)](-) (E = Te, Se, S) derivatives show the low-field shift of the amide proton ((1)H NMR (C(4)D(8)O): delta 9.66 (br) ppm (E = Te), 9.32 (br) ppm (E = Se), 8.98 (br) ppm (E = S)). The formation of the dimetallic [(CO)(3)Mn(mu-SC(8)N(2)H(4)-o-S-)](2)(2-) can be interpreted as coordinative association of two units of unstable mononuclear [(CO)(3)Mn(-SC(8)N(2)H(4)-o-S-)](-) and reflects the pi-donating ability of the bidentate ligand is responsible for the formation of pentacoordinate, sixteen-electron manganese(I) carbonyl complexes. The neutral bimetallic manganese(I)-bismercaptophenyl disulfide complex [(Mn(CO)(3))(2)(mu-SC(6)H(4)-o-S-S-C(6)H(4)-o-mu-S-)] with internal S-S bond length of 2.222(1) A and the five-coordinate sixteen-electron complex [Mn(CO)(3)(-SC(6)H(4)-o-S-)](-) are chemically interconvertible. In a similar fashion, treatment of complex [Mn(CO)(3)(-SC(6)H(4)-o-NH-)](-) with HBF(4) yielded neutral dinuclear complex [(CO)(3)Mn(mu-SC(6)H(4)-o-NH(2)-)](2) and showed that the amine deprotonation is reversible. Investigations of pi-donating ligand metathesis reactions of complex [Mn(CO)(3)(-TeC(6)H(4)-o-NH-)](-) revealed that the stable intermediate, not the pi-donating ability of bidentate ligands, is responsible for the final protonation/oxidation product. This argument is demonstrated by reaction of [Mn(CO)(3)(-TeC(6)H(4)-o-NH-)](-) with 1,2-benzenedithiol, hydroxythiophenol, and catechol, respectively leading to the formation of [Mn(CO)(3)(-EC(6)H(4)-o-E'-)](-) (E = S, O; E' = S, O), although any pi-donor containing the amido group is a more effective donor than any other pi-donor lacking an amido group. Also, the reactions of [Mn(CO)(3)(-TeC(6)H(4)-o-NH-)](-) with electrophiles occurring at the more electron-rich amide site support that the more electron-rich amide donor of the chelating 2-tellurolatophenylamido occupies an equatorial site as indicated by a shorter Mn(I)-N bond length of the distorted trigonal bipyramidal [Mn(CO)(3)(-TeC(6)H(4)-o-NH-)](-).

Bis(pyrazol-1-yl)acetates as tripodal “scorpionate” ligands in transition metal carbonyl chemistry: syntheses, structures and reactivity of manganese and rhenium carbonyl complexes of the type [LM(CO) 3] (L=bpza, bdmpza)

The coordination of the ligands bis(3,5-dimethylpyrazol-1-yl)acetate (bdmpza) and bis(pyrazol-1-yl)acetate (bpza) to Group VII metal carbonyls has been investigated. The compounds [LM(CO) 3], where M=Mn, Re and L=bpza, bdmpza ( 2a– 3b), have been synthesised. The new complexes [(bdmpza)Mn(CO) 3] ( 2b), [(bpza)Re(CO) 3] ( 3a) and [(bdmpza)Re(CO) 3] ( 3b), and bis(pyrazol-1-yl)acetic acid ( 1a) have been characterised by single-crystal X-ray analyses. Based on IR-spectroscopic and structural data the electronic properties of these ligands are compared with those of Tp, Tp Me 2 , Cp and Cp*. The reaction of [(bdmpza)Re(CO) 3] ( 3b) with NOBF 4 afforded [(bdmpza)Re(CO) 2(NO)]BF 4 ( 4).

Synthesis of and Small Molecule Coordination to Highly Electrophilic Cationic Manganese(I) and Rhenium(I) Carbonyl Complexes with Tied-Back Phosphites

Formally 16e highly electrophilic fragments [Mn(CO)4(L)][BArF] with a tied-back phosphite (L = P(OCH2)3CMe) coordinate Et2O (5b) or cis-cyclooctene (5c) and are prepared by reaction of the neutral methyl complex Mn(Me)(CO)4(L) with [H(OEt2)2][BArF] or [Ph3C][BArF] in the presence of cis-cyclooctene (cco), respectively. The solvent-bound rhenium complexes [Re(CO)4(L)(CH2Cl2)][BArF] (6a) and [Re(CO)3(L)2(CH2Cl2)][BArF] (7a) are prepared similarly by reaction of the respective neutral precursors with [Ph3C][BArF] in CH2Cl2. The CH2Cl2 molecule binds tightly to the Re(I) center and could not be removed under high vacuum for hours. However, the CH2Cl2 is readily displaced by Et2O, cco, and Et3SiH to afford ether-, olefin-, and silane-coordinated complexes 6b−d and 7b−d, respectively. While the η2-(H−SiEt3)-coordinated 7d is stable in solution at room temperature and is a rare example of an isolable cationic silane complex, the more electrophilic analogue 6d readily decomposes at room temperature to give the hydride-bridged complex {[cis-Re(L)(CO)4]2(μ-H)}{BArF} (10). Solid-state structures of 5c, 10, and 7b have been determined by single-crystal X-ray structural analysis.

13C,17O and55Mn NMR studies on substituted manganese carbonyl complexes. A contribution to the mechanism of demetalation reactions

13C and 17O chemical shifts and 55Mn,13C coupling constants of nine pentacarbonylmanganese complexes RMn(CO)5 (6–14), 13 tetracarbonylmanganese complexes RMn(CO)4PR3′ (15–27) and five tetracarbonylmanganacycle complexes (1a–e) were determined and are discussed in terms of σ-inductive substituent effects on axial and equatorial CO ligands. Linear correlations are observed between σI(R) and δ(13C) of equatorial CO ligands and δ(17O) of axial CO ligands, respectively. In the tetracarbonylmanganacycle complexes 1a–e the 17O chemical shifts of the axial (CO)a ligands exhibit the largest substituent effect (trans influence), they correlate with the rates log kobs of the demetalation reaction and the mechanistic implications are discussed. The 55Mn,13C coupling constants of the axial (CO)a ligands (144–159 Hz) likewise show a large and steady substituent dependence. © 1998 John Wiley & Sons, Ltd.

13C, 17O and 55Mn NMR studies on substituted manganese carbonyl complexes. A contribution to the mechanism of demetalation reactions

13C, 17O and 55Mn NMR studies on substituted manganese carbonyl complexes. A contribution to the mechanism of demetalation reactions

Complexes of Distibinomethane Ligands. 1. Iron, Cobalt, Nickel, and Manganese Carbonyl Complexes

The reaction of Fe2(CO)9 in thf with Ph2SbCH2SbPh2 (dpsm) or Me2SbCH2SbMe2 (dmsm) produced [Fe(CO)4(η1-dpsm)] and [Fe(CO)4(μ-dmsm)Fe(CO)4], and Co2(CO)8 reacted with either distibine ligand (L-L) to give [Co2(CO)4(μ-CO)2(μ-L-L)]. Ni(CO)4 and dpsm gave [Ni(CO)3(η1-dpsm)] and [Ni(CO)3(μ-dpsm)Ni(CO)3], while with dmsm only [Ni(CO)3(μ-dmsm)Ni(CO)3] was isolated. Mn2(CO)10 reacted slowly with dpsm or dmsm in the presence of a [{(Cp)Fe(CO)2}2] catalyst to give [Mn2(CO)8(L-L)], but no reaction occurred with Re2(CO)10 under similar conditions. cis-[Mn(CO)4X(dpsm)] (X = Cl, Br, or I) and [Mn2(CO)8Br2(μ-dmsm)] were also prepared from the appropriate [Mn(CO)5X], but iron carbonyl halide derivatives were too unstable to isolate in the pure state. The complexes have been characterized by elemental analysis, IR and multinuclear NMR (1H, 13C{1H}, 55Mn, or 59Co) spectroscopy, and FAB mass spectrometry. The X-ray structures of dpsm, [Fe(CO)4(η1-dpsm)], and [Co2(CO)4(μ-CO)2(μ-dmsm)] have been determined. No evidence for chelation by dmsm or dpsm was found, and Sb−C fission does not occur to significant extents in the reactions studied.