Iron carbonyl complexes protonation

Acetylene-vinylidene rearrangements of silylacetylene-iron carbonyl complexes have been observed,537 while iron-acetylide hydride complexes of the type [Fe(H)(C=CR)(dmpe)2], where dmpe=l,2-bis(dimethylphosphino)ethane, have been found to react with anions to afford substituted alkenyl complexes. It has been proposed538 that a likely reaction course for this latter rearrangement involves initial protonation of the cr-bound acetylide ligand at the carbon (I to the metal centre to form a vinylidene complex. Metal-to-carbon hydride migration in this vinylidene complex with attack by the anion would then lead to the neutral complex (see Scheme 106). A detailed mechanistic investigation has been carried out539 on the novel metathetical... 

Both complexes 39 and 40 are poor catalysts for the TH of acetophenone in basic isopropanol, suggesting that the protonated or deprotonated form is not within the catalytic cycle. When a catalytic mixture with 32 is evaluated by P NMR, the major species detected in solution is 40 along with free ligand and oxidized free ligand. Mass balance experiments, as evaluated by P NMR, showed that a maximum of 75% of the iron in solution is NMR inactive, suggesting that the active species is either NMR inactive or NMR active and found in extremely low concentrations. Furthermore, an IR spectmm of a cmde solution of 40 revealed two distinct carbonyl stretching frequencies at 1862 and 1870 cmwhich are indicative of electron-rich iron carbonyl complexes. 

In a remarkable synthetic feat, Tard et al. reported in 2005 the constmction of the complete six-iron metallosulfur framework of the [FeFe]-hydrogenase H-cluster shown as complex 2 in Figure 6.5 [104]. However, this compound differs from the enzyme active site in that it does not feature a rotated structure with an open apical coordination site and abridging carbonyl ligand. Such a rotated structure is now thought to be one of the necessary features for efficient catalysis by the iron carbonyl complexes because it promotes protonation at a terminal coordination site instead of a bridging position. As expected, based on these grounds, the model in this experiment is an unremarkable catalyst. 

Treatment of the potentially electrophilic Z-xfi-unsaturated iron-acyl complexes, such as 1, with alkyllithium species or lithium amides generates extended enolate species such as 2 products arising from 1,2- or 1,4-addition to the enone functionality are rarely observed. Subsequent reaction of 2 with electrophiles results in regiocontrolled stereoselective alkylation at the a-position to provide j8,y-unsaturated products 3. The origin of this selective y-deproto-nation is suggested to be precoordination of the base to the acyl carbonyl oxygen (see structures A), followed by proton abstraction while the enone moiety exists in the s-cis conformation23536. 

Completely different behavior toward liquid NH3 is shown by the three iron carbonyls Fe(CO)s, Fe3(CO)9, and Fes(CO),2 (98, 99) and the two cobalt carbonyls Co2(CO)8 and Co4(CO)i3 (100). Between -21 and 0°C, Fe(CO)5 and liquid NH3 give a homogeneous, pale-yellow solution from which Fe(CO)5 may be recovered on evaporating off the NH3. The solution contains the carbamoyl complex NHJfOC Fe—CONHJ which cannot be isolated and which is formed by nucleophilic attack of an NH3 molecule on a CO ligand, followed by proton release (101). At 20°C after 14 days of reaction, (NHJ FefCOlJ and CO(NH2)2 are obtained (99) ... 

Similarly protonation of diphenylfulveneiron tricarbonyl generates a substituted 7r-cyclopentadienyl cation (241, 242). Hydride abstraction from cyclopentadieneiron tricarbonyl releases the 77-cyclopentadienyl cation complex (172). The Mossbauer spectra of the [CpFe(CO)3]1 cation and related iron carbonyl cations have been determined (121). 

By reaction of cationic carbonyl complexes with lithium carbanions, neutral acyl complexes are prepared. Whereas treatment of [> -CpFe(CO)3]BF4 with (a) PhLi gives the expected > -CpFe(CO)2 [C(0)Ph] in 80% yield, with (b) MeLi only traces of > -CpFe(CO)2 [C(0)Me] can be detected . This complex and other phosphane-substituted acyl compounds of the type f -CpM(CO)L[C(0)Me] [M = Fe, Ru L = CO, PPh3, P(hex)j], as well as >/ -CpMo(CO)2P(hex)3[C(0)Me] (prepared by different routes), are protonated with and alkylated with [R3 0]BF4 reversibly, yielding cationic hydroxy- and alkoxy(methyl)carbene complexes, respectively . The formation of the ( + )- and ( —)-acetyl complex / -CpFe(C0)(PPh3)[C(0)Me] from the ( + )-and ( —)-conformers of optically active > -CpFe(C0XPPh3)[C(0)0-menthyl] and MeLi occurs with inversion of configuration at the asymmetric iron atom . 

The w-(C4)M system has also been observed in ring systems in which a father simpler situation from the spectroscopic viewpoint exists than in the parent olefin. Two such examples are the complexes of cyclopentadienone (XXI) or the unusual binuclear complex obtained from an iron carbonyl and acetylene, C4H4- Fe2(CO)6 (XXII) (Table XV). The proton resonances in these complexes may be analysed simply as A2B2 systems. Details on the structures, especially the position of the protons in these complexes, is not yet known. 

Many carbonyl and carbonyl metallate complexes of the second and third row, in low oxidation states, are basic in nature and, for this reason, adequate intermediates for the formation of metal— metal bonds of a donor-acceptor nature. Furthermore, the structural similarity and isolobal relationship between the proton and group 11 cations has lead to the synthesis of a high number of cluster complexes with silver—metal bonds.1534"1535 Thus, silver(I) binds to ruthenium,15 1556 osmium,1557-1560 rhodium,1561,1562 iron,1563-1572 cobalt,1573 chromium, molybdenum, or tungsten,1574-1576 rhe-nium, niobium or tantalum, or nickel. Some examples are shown in Figure 17. 

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