COD Complexes Research Articles

Structures, Thermal Properties, and Reactivities of Cationic Rh-cod Complexes in Solid State (cod = 1,5-Cyclooctadiene).

Cationic rhodium complexes with 1,5-cyclooctadiene (cod) ligands are important organometallic compounds that are useful as precatalysts; however, their solid-state structures and thermal properties have not been adequately investigated. In this study, we synthesized [Rh(cod)L]X (L = cod, C6H6, PhMe; X = SbF6, (FSO2)2N (= FSA), CF3BF3, CB11H12) and investigated their phase behaviors, crystal structures, and reactivities. The phase transitions of these salts result in disordered solid-state structures. Moreover, the structural disorder increases with a decrease in the cation symmetry in the SbF6 salts; [Rh(cod)(PhMe)]SbF6 exhibits a rotator phase, and the cations in other salts exhibit a dynamic rotational disorder. In contrast, a lower crystal symmetry with less cation disorder is observed for FSA salts. The thermal stabilities and reactivities of these salts were further investigated. FSA salts with arene ligands produce anion-coordinated complexes upon melting, and SbF6 salts with arene ligands produce [Rh(cod)L'2]SbF6 (L' = MeCN and SMe2) via an in situ single-crystal-to-single-crystal ligand-exchange reaction.

Iridium complexes with P-stereogenic phosphino imidazole ligands: Synthesis, structure and catalysis

The synthesis of optically and diastereomerically pure P-stereogenic phosphine-imidazole ligands is reported. The new ligands contain either a benzoimidazole or a 4-phenylimidazole as a N-donor fragment. The ligands have been coordinated to iridium and the structure of the corresponding cationic COD complexes has been determined by X-ray analysis. The combination of the chiral phosphorus atom and the imidazole substituents generate a strong chiral environment around the metal center. Preliminary hydrogenation reactions with a model cyclic β-enamide are also reported.

N-heterocyclic carbenes bearing a naphthyl substituent and their metal complexes: synthesis, structure, and application in catalytic transfer hydrogenation

A series of unsymmetrical imidazolinium bromides (3a-d) bearing naphthyl and benzyl groups (R' = CH$_{2}$C$_{6}$H$_{2}$(CH$_{3})_{3}$-2,4,6 (a); CH$_{2}$C$_{6}$H(CH$_{3})_{4}$-2,3,5,6 (b); CH$_{2}$C$_{6}$(CH$_{3})_{5}$ (c); CH$_{2}$C$_{6}$F$_{5\, }$(d)) at the N$^{1}$ and N$^{3}$ positions were successfully synthesized. [RuCl$_{2}$(NHC)($p$-cymene)] (NHC= N-heterocyclic carbene) complexes (4a-d) were prepared by the reaction of [RuCl$_{2}(p$-cymene)]$_{2}$ with imidazolinium salts (3a-d). The new salts (3a-d) and their ruthenium(II) complexes (4a-d) were characterized by $^{1}$H, $^{13}$C, $^{19}$F NMR, and elemental analysis. The ruthenium(II) complexes (4a-d) were employed as catalysts for the transfer hydrogenation (TH) of ketones in the presence of KOH using 2-propanol as a hydrogen source and the results were compared. The best results in the transfer hydrogenation of ketones were obtained with 4b. [MCl(NHC)L] (M = Ir, L = Cp$^{\ast })$ (5b), cod (6b); M = Rh, L= Cp$^{\ast}$ (5b'), and cod (6b') complexes were prepared and investigated in the TH of ketones. The reactivity of Rh complexes in comparison to those of Ir also appears to be somewhat better. The catalysis appears to be homogeneous.

Characterization and oxidative addition reactions for iridium cod complexes

Three different [Ir(LL′)(cod)] complexes (LL′ = N-aryl-N-nitrosohydroxylaminato) (cupf), trifluoroacetylacetonato (tfaa), and (methyl 2-(methylamino)-1-cyclopentene-1-dithiocarboxylato-κN,κS) (macsm)) were synthesized, characterized, and their rates of oxidative addition with methyl iodide were determined. Formation of an isosbestic point during the oxidative addition of methyl iodide with the complexes containing tfaa and cupf as bidentate ligands indicated formation of only one product, while an increase in absorbance maximum observed for macsm confirms that the same reaction between the complex and methyl iodide occurs. Kinetic results for all complexes, except [Ir(tfaa)(cod)], showed simple second-order kinetics with a zero intercept (within experimental error). Rates of oxidative addition for bidentate ligands in acetonitrile showed an increase of an order of magnitude with a change in the type of bidentate ligands. Computational chemistry using density functional theory calculations showed that the oxidative addition reaction proceeds through a “linear” transition state with the methyl iodide unit tilted towards the LL′-bidentate ligand.

Preparation, structure, and dynamic and electrochemical behaviors of dinuclear rhodium(I) complexes with bridging formamidinato ligands

Dinuclear rhodium(I) complexes, [Rh(4-Me-pf) (cod)]2 (1), [Rh(3,5-Me2-pf) (cod)]2 (2), [Rh(4-Me-pf) (nbd)]2 (3), [Rh(3,5-Me2-pf) (nbd)]2 (4), and [Rh(2,6-F2-pf) (nbd)]2 (5), have been synthesized and characterized by X-ray structure analysis, 1H, 13C, and 19F NMR, UV–vis, ESI-TOF-MS, and elemental analysis. In these complexes, two rhodium atoms are bridged by two formamidinato ligands and each rhodium atom is coordinated by one chelating cod or nbd ligand to form an approximately square planar coordination structure with two nitrogen atoms and two double bonds. The Rh··Rh distances are in the range of 3.2668 to 2.9726 Å, suggesting a direct bonding interaction between two rhodium atoms. Variable temperature NMR studies in CD2Cl2 solution have revealed that 1–5 exhibit a novel dynamic behavior, that is, an interconversion between two enantiomers. The activation parameters for racemization have been determined by the line shape analyses of the 1H and 19F NMR spectra taken at various temperatures. Variable temperature NMR studies have also revealed that the rotation rates of the four aryl groups around N–C(aryl) bonds are extremely different in each complex. The cyclic voltammetry study has shown that the oxidation potentials corresponding to Rh23+/Rh2+ are 0.41 V in the cod complexes (1 and 2) while those in the nbd complexes (3–5) have shown negative shift by ca. 0.2 V. The reasons for the difference in dynamic behaviors and redox properties among these complexes have been discussed.

Comparative study of electronic and steric properties of bulky, electron-rich bisphosphinoethane, bis-NHC and phosphino-NHC chelating ligands in analogous rhodium(I) and iridium(I) COD and carbonyl complexes

The synthesis and characterization of rhodium(I) and iridium(I) COD (1,5-cyclooctadiene) and carbonyl complexes containing small-bite angle and bulky bisphosphine (bis(di-tert-butylphosphino)ethane = dtbpe), bis-NHC (1,1′-di-tert-butyl-3,3′-methylenediimidazolin-2,2′-ylidene = BisNHC) and phosphino-functionalized NHC (3-tert-butyl-1-(di-tert-butylphosphinomethyl)-imidazolin-2-ylidene = NHCP) ligands is described. X-ray diffraction analysis of most compounds made and spectroscopic data permitted a valuable comparison of the characteristic steric and electronic properties of these related ligand classes and also of the “abnormally” bound form of the NHCP ligand (aNHCP). While the dicarbonyl complexes indicated similar overall donating abilities for the BisNHC and NHCP ligands, dtbpe and the aNHCP ligand were shown to be significantly less or more electron donating, respectively. These complexes also allowed the evaluation of the different σ-donating influences of the NHC moiety in comparison to the phosphine moiety within the hybrid NHC–P systems.

ChemInform Abstract: Iridium(I) Complexes with Anionic N‐Heterocyclic Carbene Ligands as Catalysts for the Hydrogenation of Alkenes in Nonpolar Media.

A series of lithium complexes of anionic N-heterocyclic carbenes that contain a weakly coordinating borate moiety (WCA-NHC) was prepared in one step from free N-heterocyclic carbenes by deprotonation with n-butyl lithium followed by borane addition. The reaction of the resulting lithium-carbene adducts with [M(COD)Cl]2 (M = Rh, Ir; COD = 1,5-cyclooctadiene) afforded zwitterionic rhodium(I) and iridium(I) complexes of the type [(WCA-NHC)M(COD)], in which the metal atoms exhibit an intramolecular interaction with the N-aryl groups of the carbene ligands. For M = Rh, the neutral complex [(WCA-NHC)Rh(CO)2] and the ate complex (NEt4)[(WCA-NHC)Rh(CO)2Cl] were prepared, with the latter allowing an assessment of the donor ability of the ligand by IR spectroscopy. The zwitterionic iridium–COD complexes were tested as catalysts for the homogeneous hydrogenation of alkenes, which can be performed in the presence of nonpolar solvents or in the neat alkene substrate. Thereby, the most active complex showed excellent s...

Strong Cytotoxicity of Organometallic Platinum Complexes with Alkynyl Ligands

The synthesis, spectroscopy, structures, and chemical reactivity of the organometallic complexes [(COD)Pt(C≡CR)2] and [(COD)Pt(C≡CR)(R′)] (COD = 1,5-cyclooctadiene, R = Ph, (Me)Ph (2Me, 3Me, or 4Me), (NO2)Ph (2NO2, 3NO2, or 4NO2), (4F)Ph, (4OMe)Ph, 2Py (2-pyridyl); R′ = Me (methyl), Neop (neopentyl = 2,2-dimethyl-1-methyl), NeoSi (neosilyl = trimethylsilylmethyl), Bz (benzyl)) has been explored. The crystal structures reveal square-planar surroundings of the Pt atoms with short Pt–C(alkynyl) bonds (<2 Å) and almost perpendicular orientation of the C≡C–aryl group to the Pt coordination plane. Nonattractive π–π stacking and C–H···F intermolecular interactions were observed in the crystal structures. Multinuclear (1H, 13C, 195Pt, and 19F) NMR spectroscopy reveals structures in solution and Pt–ligand bond strength. The thermal stability in organic solvents, the electrochemical stability, and the reactivity of the complexes in organic or aquatic (water-containing) solution toward the physiologically relevant species glutathione, chloride, and protons was tested, revealing remarkable stability or inertness of the complexes. Cytotoxicity experiments in HT-29 colon carcinoma and MCF-7 breast adenocarcinoma cell lines revealed highly promising activities for selected platinum alkynyl COD complexes.

Isomerism in rhodium(i) N,S-donor heteroscorpionates: ring substituent and ancillary ligand effects

The heteroscorpionate ligands [HB(taz)(2)(pz(R))](-) (pz(R) = pz, pz(Me2), pz(Ph)) and [HB(taz)(pz)(2)](-), synthesised from the appropriate potassium hydrotris(pyrazolyl)borate salt and 4-ethyl-3-methyl-5-thioxo-1,2,4-triazole (Htaz), react with [{Rh(cod)(μ-Cl)}(2)] to give [Rh(cod)Tx] {Tx = HB(taz)(2)(pz), HB(taz)(2)(pz(Me2)), HB(taz)(2)(pz(Ph)), HB(taz)(pz)(2)}; the heteroscorpionate rhodaboratrane [Rh{B(taz)(2)(pz(Me2))}{HB(taz)(2)(pz(Me2))}] is the only isolable product from the reaction of [{Rh(nbd)(μ-Cl)}(2)] with K[HB(taz)(2)(pz(Me2))]. Carbonylation of the cod complexes gave a mixture of [Rh(CO)(2)Tx] and [(RhTx)(2)(μ-CO)(3)] which reacts with PR(3) to give [Rh(CO)(PR(3))Tx] (R = Cy, NMe(2), Ph, OPh). In the solid state the complexes are square planar with the particular structure dependent on the steric and/or electronic properties of the scorpionate and ancillary ligands. The complex [Rh(cod){HB(taz)(pz)(2)}] has the heteroscorpionate κ(2)[N(2)]-coordinated to rhodium with the B-H bond directed away from the rhodium square plane while [Rh(cod){HB(taz)(2)(pz(Me2))}] is κ(2)[SN]-coordinated, with the B-H bond directed towards the metal. The complexes [Rh(CO)(PPh(3)){HB(taz)(2)(pz)}] and [Rh(CO)(PPh(3)){HB(taz)(2)(pz(Me2))}] are also κ(2)[SN]-coordinated but with the pyrazolyl ring cis to PPh(3); in the former the B-H bond is directed towards rhodium while in the latter the ring is pseudo-parallel to the rhodium square plane, as also found for [Rh(CO)(2){HB(taz)(2)(pz(Me2))}]. The analogues [Rh(CO)(PR(3)){HB(taz)(2)(pz(Me2))}] (R = Cy, NMe(2)) have the phosphines trans to the pyrazolyl ring. Uniquely, [Rh(CO)(PPh(3)){HB(taz)(2)(pz(Ph))}] is κ(2)[S(2)]-coordinated. A qualitative mechanism is given for the rapid ring-exchange, and hence isomerisation, observed in solution.

Bimacrocyclic NHC transition metal complexes

The preparation of seven concave NHC metal complexes derived from bimacrocyclic imidazolinium salt 1 is reported. The silver complex 2, obtained in 86% yield by reacting 1 with silver(I) oxide, was used to give copper complex 3, rhodium complex 5 and iridium complex 6 by transmetalation in good yields. Palladium complex 4 was obtained by reaction of the azolium salt 1 with palladium dichloride in 3-chloropyridine. The rhodium and iridium dicarbonyl complexes 7 and 8 were prepared via ligand exchange from the COD complexes 5 and 6. Silver complex 2, copper complex 3 and palladium complex 4 were characterized by single-crystal X-ray analysis. Silver complex 2 and copper complex 3 were tested in the cyclopropanation of styrene and indene with EDA (ethyl diazoacetate), where good results were obtained with 3, while low conversion and catalyst decomposition was observed with 2.

Synthesis of a Library of Iridium-Containing Dinuclear Complexes with Bridging PNNN and PNNP Ligands (BL), [LM(μ-BL)M‘L‘]BF4. 2. Preparation, Basic Coordination Properties, and Reactivity of the Carbonyl Complexes

A series of dinuclear carbonyl complexes with PNNP and PNNN ligands, [(L)M(PNNX)M'(L)]BF 4 (X = P, N; M(L), M'(L') = Ir(CO) 2 , Rh(CO) 2 , Pd(allyl)), have been prepared by carbonylation (1 atm) of the corresponding cod complexes, and the Rh/Ir complexes have been further converted to μ-η 1 :η 2 -acetylide complexes, where effective π-back-donation to the acetylide ligand is essential to stabilize them. On the basis of the stability of the acetylide complexes, the π-donating ability of the metal fragment in the PNNX system is estimated to be (P,N)Rh > (P,N)Ir > (N,N)M. The dinuclear PNNX complexes catalyze alkyne hydrogenation, alkene hydroformylation, and allylation of aniline with allyl alcohol, and, for the allylation, a dinuclear mechanism involving activation of allyl alcohol by interaction with a CO ligand is proposed.

Structure Dynamics and Isomerism of Bis[μ-(2-methylphenolato)]bis[(η2:η2-cycloocta-1,5-diene)rhodium(I)] Complex

Dinuclear rhodium(I) complex [{RhI(cod)}2(μ-OC6H4-2-Me)2] (1), exhibits the syn-anti isomerism consisting in the orientation of methyl groups of the bridge ligands with respect to the plane or distorted plane involving Rh and O atoms. The syn isomer predominates in CDCl3 solution (above 90%) at room temperature. EXSY 1H NMR measurements showed that, in CDCl3 solution, complex 1 undergoes at least two independent dynamic processes differing substantially in values of activation parameters: (i) rotation of 2-methylphenyl rings in bridge ligands along the O-C axis, and (ii) formal rotation of cod ligands along the Rh-cod axes, which proves fluxional behavior of cod ligand in RhI(cod) complexes.

Platinum(II) and Palladium(II) Dibenzo[a,e]cyclooctatetraene (DBCOT) Oxo and Halide Complexes: Comparison to 1,5-COD Analogues

The dialkene complexes L2MCl2 (M = Pt, Pd, L2 = dibenzo[a,e]cyclooctatetraene (DBCOT)) were prepared by treatment of MCl42- salts with L2. Comparison of the solid-state structures with those of the analogous 1,5-cyclooctadiene (COD) complexes shows strong congruence of the structures. Competition experiments between DBCOT and COD show that COD bonds more strongly to the Pt(II) center. In contrast, Ir(I) bonds slightly better to DBCOT. Reaction of PtCl2(DBCOT) with NaI gives PtI2(DBCOT), which reacts with PhMgBr to give PtPh2(DBCOT). 195Pt NMR data indicate a less electron-rich Pt center in the DBCOT complexes as compared to the analogous COD complexes. Treatment of PtCl2(DBCOT) with [(Ph3PAu)3(μ3-O)](BF4) yields trimeric [Pt(μ3-O)(DBCOT)(AuPPh3)]3(BF4)3, which contains a six-membered Pt3O3 ring in a twist-boat configuration. Au−Au and Au−Pt interactions may help stabilize the solid-state structure, but NMR and mass spectral data indicate a dynamic structure in solution and the likely presence of other oli...

Conformational behaviour of dinuclear Rh(I) complexes of the open-chain tetrapyrrolic ligand 2,2′-bidipyrrin (H 2BDP)

The reaction of 2,2′-bidipyrrins H 2BDP with the Rh I complexes [Rh(COD)(μ-OMe)] 2 and [Rh(CO) 2(μ-Cl)] 2 yields the neutral species [{Rh(COD)} 2BDP] ( 7, 8) and [{Rh(CO) 2} 2BDP] ( 2, 9), respectively. Treatment of the COD complexes with carbon monoxide results in the exchange of all COD ligands against CO. Ligand exchange studies on the carbonyl complexes 2 and 9 with different phosphane donors reveal the regioselective exchange of one CO per metal ion. In most cases, the reaction is accompanied by a large conformational change of the tetrapyrrole from a syn to an anti conformation. This conformational change was resolved by a combination of NMR spectroscopy and X-ray diffraction studies.

Mechanism of Oxidation of (olefin)RhI and ‐IrI Complexes by H2O2

AbstractA DFT study of the oxidation of (tpa)MI(C2H4)+ and (dpa‐R)MI(cod)+ complexes (M = Rh, Ir) by H2O2 indicates that the reaction starts with heterolytic cleavage of the peroxide O−O bond, leading to MIII(olefin)(OH)2+ species. These can then undergo cyclisation, followed by deprotonation to oxetanes. In the oxidation of COD complexes, further cyclisation to internal ethers has a modest barrier, and the observed products (ethers for Rh, oxetanes for Ir) are suggested to be the thermodynamic ones. (© Wiley‐VCH Verlag GmbH &amp; Co. KGaA, 69451 Weinheim, Germany, 2004)

Synthesis and reactivity of substituted cyclopentadienyl rhodium(I) and (III) complexes

New cyclopentadienyl derivatives of rhodium COD complexes [Cp*=C 5H 4COOCH 2CHCH 2 ( 1); C 5H 4CH 2CH 2CHCH 2 ( 2); C 5H( i-C 3H 7) 4 ( 3)] and carbonyl complex [Cp*=C 5H( i-C 3H 7) 4 ( 4)] were synthesized from [RhCl(COD)] 2 and [RhCl(CO) 2] 2. 1, 2 and 3 oxidized by iodine gave iodine bridged dimers 5, 6 and 7, respectively. Triphenyl phosphine, carbon monoxide and carbon disulfide molecules broke down the iodine bridged structure easily and produced monomer products Cp*RhI 2L [Cp*=C 5H 4COOCH 2CHCH 2, L=CS 2 ( 8); L=PPh 3 ( 9). Cp*=C 5H( i-C 3H 7) 4, L=CO ( 10)]. All of these new compounds were characterized by elemental analysis, 1H NMR, IR, UV–Vis and mass spectroscopy. The crystal structure of 1 was solved in the triclinic space group P 1 ̄ with one molecule in the unit cell, the dimensions of which are a=7.082(9) Å, b=8.392(3) Å, c=13.889(5) Å, α=101.19(3)°, β=99.06(6)°, γ=105.11(5)°, and V=763(1) Å 3. The crystal structure of 3 was solved in the orthorhombic space group Pn21 a with four molecules in the unit cell, the dimensions of which are a=9.748(3) Å, b=16.054(5) Å, c=14.816(4) A ̊ and V=2319(1) Å 3. Least squares refinement leads to values for the conventional R 1 of 0.0251 for 1 and 0.0558 for 3, respectively. Compared to that in 1, a shorter metal–ligand bond length in 3 was observed and this is attributed to the rich electron density on Rh(I) metal center piled up by the C 5H( i-C 3H 7) 4 ligand.

Synthesis and Characterization of Ruthenium Complexes with Two Fluorinated Amino Alkoxide Chelates. The Quest To Design Suitable MOCVD Source Reagents

The synthesis and characterization of ruthenium complexes [Ru(CO)2(amak)2] and [Ru(COD)(amak)2] (where COD = 1,4-cyclooctadiene) are reported, where (amak)H is an abbreviation for a series of fluorinated amino alcohol ligands with formula HOC(CF3)2CH2NHR, where R = H, Me, Et, and (CH2)2OMe. The carbonyl complex [Ru(CO)2(amak1)2] (1 with R = H) was examined by X-ray diffraction (XRD), showing an octahedral coordination for the Ru atom, with two cis carbonyl ligands and two amino alkoxide chelates. For the COD complexes [Ru(COD)(amak1)2] (3 with R = H) and [Ru(COD)(amak3)2] (4 with R = Et), the structural analysis indicated the existence of two distinct spatial arrangements of amino alkoxide chelates with respect to the coordinated COD ligand, depending on the type of amino group selected. All of these complexes show good volatility and thermal stability. For complexes 2 and 4, which are more volatile and low-melting, chemical vapor deposition (CVD) experiments were conducted at temperatures of 325−425 °C, ...

Amido-bridged dinuclear rhodium(I) complexes by deprotonation of mononuclear rhodium(I) amine complexes

The preparation of a series of new amido bridged binuclear complexes [(NNN)RhI2(cod)2] (cod=Z,Z-1,5-cyclooctadiene), [(NNN)RhI2(hed)2] (hed=1,5-hexadiene) and [(NNN)RhI2(CO)4] is reported. These complexes contain chelating imidazoleamidoimidazole, pyridineamidopyridine and pyridineamidopyrrolate ligands (NNN). The cod complexes have been prepared through deprotonation of their mononuclear amine precursors [(NHNN)RhI(cod)] in the presence of [RhI(cod)]+. Reaction of the binuclear complexes [(NNN)RhI2(cod)2] with CO results in the complexes [(NNN)RhI2(CO)4]. For NNN chelating imidazoleamidoimidazole ligand, the X-ray structures of [(NNN)RhI2(cod)2], [(NNN)RhI2(CO)4], and their mononuclear amine precursor [(NHNN)RhI(cod)] are reported. Electrochemical oxidation of the complexes is related to the relative donor strength of the N-ligands.

Structures, Reactivity, and Catalytic Activity of Dithiolato-Bridged Heterobimetallic MRh (M = Pt, Pd) Complexes

Heterobimetallic complexes [(P−P)Pt(μ-S−S)Rh(cod)]ClO4 (P−P = (PPh3)2, Ph2P(CH2)3PPh2 (dppp), and Ph2P(CH2)4PPh2 (dppb); S−S = -S(CH2)2S- (EDT), -S(CH2)3S- (PDT), -S(CH2)4S- (BDT), cod = 1,5-cyclooctadiene) reacted with CO to form the carbonyl complexes [(P−P)Pt(μ-S−S)Rh(CO)2]ClO4 and then with PR3 ligands to give [(P−P)Pt(μ-S−S)Rh(CO)(PR3)]ClO4. The binuclear framework of these cod complexes was maintained in the reactions reported. The cod complexes were tested as catalyst precursors in the hydroformylation of styrene. HPNMR in situ studies showed that mononuclear species formed under catalytic conditions.

An Examination of the Coordination Chemistry of L2Pt(1,2-DITHIOLENES) Using Atmospheric Pressure Chemical Ionization Mass Spectrometry

Atmospheric pressure chemical ionization mass spectrometry (APCI–MS) has been utilized in the characterization of two series of platinum dithiolene complexes, (COD)Pt(dt) 1, (COD)–Pt(edt) 2, (COD)Pt(dmid) 3, (COD)Pt(mnt) 4, (COD)Pt(eddo) 5, (COD)Pt(dddt) 6 and (Ph3P)2Pt(dt) 7, (Ph3P)2Pt(edt) 8, (Ph3P)2Pt(dmid) 9, (Ph3P)2Pt(dmit) 10, (Ph3P)2Pt(mnt) 11 (where COD = 1,5–cyclooctadiene, dt = ethane–1,2–dithiolate, edt = ethylene–1,2–dithiolate, dmid = 1,3–dithiole–2–oxo–4,5–dithiolate, dmit = 1,3–dithiole–2–thione–4,5–dithiolate, mnt = maleonitrile–1,2–dithiolate, eddo = 4–(ethylene–1′,2′–dithiolate)–1,3-dithiole–2–one, and dddt = 5,6–dihydro–1,4–dithiin–2,3–dithiolate). The series that contains triphenylphosphine is labile toward the loss of HPPh3 +. In addition, an orthometallated species involving the platinum and triphenylphosphine is identified. A dimer is identified for 2, which is shown to be a product of the experiment and not present in the parent material. In addition, a 1:1 adduct with NH4 + is identified for 4 and 11 where the NH4 + originates from the acid hydrolysis of acetonitrile. Finally, a highly unique ion, Pt+, a bare platinum ion, is observed in all COD complexes indicating that a radical mechanism must accompany the decomposition of the COD complexes during the fragmentation process.