Carbon monoxide complexes, reversible

Knowing that carbon monoxide complexes of hemes are dissociated by light, Warburg and Negelein, in 1928, determined the photochemical action spectrum (see Chapter 23) for reversal of the carbon monoxide inhibition of respiration of the yeast Torula utilis. The spectrum closely resembled the absorption spectrum of known heme derivatives (Fig. 16-7). Thus, it was proposed that 02, as well as CO, combines with the iron of the heme group in the Atmungsferment. 

For systems that are naturally and reversibly photosensitive such as the carbon monoxide complexes of heme proteins [18,. 30, 31], initiation by a light pulse is possible. By preparation of inert but photoactivable reactant or cofactor precursors such as caged ATP [32-34], photosensitivity may be conferred on otherwise photoinert systems [21], thus extending the generality of this approach. This approach was first combined with x-ray monitoring by Blasie [35, 36], in studies of oriented multilayers containing the Ca2+-ATPase from sarcoplasmic reticulum. 

The first example shows the drastic shortening of the iron-iron separation that accompanies carbon monoxide loss. The Fe Fe separation decreases from 3.90 A in the reactant to 2.661(1) in the product.The product of reaction 11 has a Ni-Ni separation of only 2.508 A. The geometric details for the other compounds in these reactions are not known. The loss of carbon monoxide is reversible for the nickel complex. 

The first and rate-determining step involves carbon monoxide dissociation from the initial pentacarbonyl carbene complex A to yield the coordinatively unsaturated tetracarbonyl carbene complex B (Scheme 3). The decarbonyla-tion and consequently the benzannulation reaction may be induced thermally, photochemically [2], sonochemically [3], or even under microwave-assisted conditions [4]. A detailed kinetic study by Dotz et al. proved that the initial reaction step proceeds via a reversible dissociative mechanism [5]. More recently, density functional studies on the preactivation scenario by Sola et al. tried to propose alkyne addition as the first step [6],but it was shown that this... 

The A-frame hydride [Pt2H2(/i-H)(/i-dppm)2] undergoes reductive elimination of H2 in the presence of tertiary phosphine ligands, L, to give the platinum(I) dimer, [Pt2HL(//-dppm)2]. Hill and Puddephatt have shown that this occurs via the intermediate [Pt2II2(/i-H)L(//-dppm)2] (14).99 Carbon monoxide reacts rapidly and reversibly with [PtH(/r-PP)2Pt(CO)]+, PP = R2P-CH2-PR2, R = Et or Ph, to give [PtH(/i-PP)2Pt(CO)2]+ and [PtH(CO)(/u-PP)2Pt(CO)2]+, the first reported mixed valence, platinum(0)-platinum(ll) complexes.100... 

The compound [HRh(C0)(TPPTS)3] is a "precatalyst" and dissociates to the 16e species [HRh(C0)(TPPTS)2]. This oxo-active complex initiates the hydroformylation cycle. Under oxo conditions (presence of CO/H2, H20, and a surplus of TPPTS) the hydroxo complex [(HO)Rh(CO)(TPPTS)2] may be formed and again reversibly converted to [HRh(C0)(TPPTS)3] (equilibrium lies almost completely towards the hydride). However, higher carbon monoxide partial pressures may cause the displacement of TPPTS by CO according to Equation 5.8. 

The Dotz reaction mechanism has received further support from kinetic and theoretical studies. An early kinetic investigation [37] and the observation that the reaction of the metal carbene with the alkyne is supressed in the presence of external carbon monoxide [38] indicated that the rate-determining step is a reversible decarbonylation of the original carbene complex. Additional evidence for the Dotz mechanistic hyphotesis has been provided by extended Hiickel molecular orbital [23, 24] and quantum chemical calculations [25],... 

In the case of the tantalum complexes 100, reversible hydrogen migration may occur at room temperature in the presence of carbon monoxide, or at 70°C with dihydrogen or dimethylphosphino ethane to afford complexes 106, 107, and 108, respectively.92,95 In contrast, the phosphametallacycle remains intact when 100 is treated with halogenated reagents such as CH3X (X = Cl, Br, I).92,95... 

Weiss studied68a the reactivity of both new complexes, and found that a variety of phosphines and phosphites would also convert the vinylcarbene complex 139 into the corresponding vinylketene complex (140), capturing one of the carbonyl ligands from the coordination sphere of the metal to become the ketene carbonyl. Only in the case of triphenylphosphine was the dicarbonyl(phosphine)vinylcarbene complex (141) isolated, which then required addition of carbon monoxide to convert it to the dicarbonyl(triphe-nylphosphine)vinylketene complex 140.a. This interconversion was reversible and proceeded quantitatively. 

The four-coordinate alkyl complex, LNiI(C0)CH3, may coordinate with carbon monoxide to regenerate the five coordinate alkyl species, and this leads to insertion to form Ni-acyl complex. This complex, LNil (CO)(COCH3), can be cleaved either by water yielding acetic acid or by methanol to give methyl acetate. However, in the presence of high iodide concentration formation of acetyl iodide may predominate (29). This step is reversible and can lead to decarbonylation under low carbon monoxide partial pressure. Similar decarbonylations of acyl halides by nickel complexes are known (34). 

Relatively few hydroformylations using supported cobalt complexes have been reported. Moffat (78, 79) showed that poly-2-vinylpyridine reversibly reacted with both Co2(CO) and HCo(CO)4, the cobalt carbonyl being displaced by excess carbon monoxide. This enabled the polymer to pick up the cobalt carbonyl at the end of the reaction and, thus, allowed it to be separated from the products by filtration. The polymer acted as a catalyst reservoir by rapidly releasing the cobalt carbonyl into solution in the presence of further carbon monoxide, so that the actual catalysis was a homogeneous process. More recently, cobalt carbonyl has been irreversibly bound to a polystyrene resin... 

Most transition metals form complexes known as carbonyls with carbon monoxide as ligands. Examples include Fe(CO)s, Fe2(CO)9, Cr(CO)6, and Rh6(CO)i6, in all of which the metal is ostensibly in the oxidation state of zero, and many mixed-ligand carbonyls such as Mn(CO)sI, CH3Mn(CO)s, and (C6H6)Mo(CO)3 are known. Such compounds have an organiclike chemistry, being essentially covalent (see Section 8.2 and Chapter 18), and the simple carbonyls such as Ni(CO)4 are volatile liquids that can be purified by fractional distillation. Of all these, however, only Ni(CO)4 (bp 43 °C) forms rapidly (and reversibly) from the elemental metal and CO gas... 

Mirkin and coworkers reported on catalytic molecular tweezers used in the asymmetric ring opening of cyclohexene oxide. In this case the early transition metal is the catalyst and rhodium functions as the structural inductor metal. The catalyst consists of two chromium salen complexes, the reaction is known to be bimetallic, and a switchable rhodium complex, using carbon monoxide as the switch. Indeed, when the salens are forced in dose proximity in the absence of CO the rate is twice as high and the effect is reversible [77]. 

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