Howard Alper

ortho-Palladated and ortho-platinated complexes of diaryl thioketones

Abstract The first sulfur-donor ligand ortho -metalated complexes of palladium and platinum have been synthesized from thiobenzophenones. A new and convenient preparation of mono-deuterio aromatic ketones is also reported.

Desulfurization and ortho-metalation reactions of dimanganese decacarbonyl

Abstract Thiobenzophenone, and 4,4′-disubstituted derivatives having moderately electron-donating (methyl, methoxy) or electron-withdrawing (fluoro) groups, react with dimanganese decacarbonyl in refluxing heptane to produce olefins (and a sulfur manganese carbonyl complex) in good yield. 4,4′-Bis(dialkylamino)thiobenzophenones reacted with the metal carbonyl to give sulfur-donor ligand ortho-metalated complexes as the major product and 4,4′-bis(dialkylamino)diphenylmethanes as by-products. A mechanistic scheme is proposed for these reactions.

Reactions of sulfines with iron and manganese carbonyls; dexoygenation vs. ortho-metalation

Abstract Diaryl sulfines react with diiron enneacarbonyl in benzene at room temperature to give thiobenzophenones and/or ortho -metalated complexes derived from the thioketones, rather than ortho -metalated complexes of sulfines. Deoxygenation of sulfines also occurred when dimanganese decacarbonyl was used as the metal carbonyl. These reactions may proceed via initial nucleophilic attack of the sulfine at a terminal metal carbonyl carbon.

ortho-metalation of ferrocene

Abstract The first example of intramolecular ortho -metalation of a metallocene by a transition metal is described.

Reactions of iron carbonyls with ylides

Abstract Phosphoranes having the structure p -XC 6 H 4 CHP(C 6 H 5 ) 3 [where X = H, CH 3 , OCH 3 ] react with iron carbonyls in dry tetrahydrofuran to give low-reasonable yields of stilbenes as well as unstable purple-red organometallic complexes, triphenylphosphineiron tetracarbonyl, and triphenylphosphine oxide. Most phosphoranes of type RCHP(C 6 H 5 ) 3 [R = alkyl] also formed unstable organometallics and (C 6 H 5 ) 3 PFe(CO) 4 , but only in two instances were the substituted ethylenes isolated in low yields. Substantial variation in the cis-trans alkene distribution and in the overall yield of alkene was observed in the reaction of Fe(CO) 5 with p -CH 3 C 6 H 4 CHP(R′) 3 , where R′ = p -FC 6 H 4 , C 6 H 5 , n-C 4 H 9 , and (CH 3 ) 2 N. The reaction of Fe(CO) 5 with C 6 H 5 COCH − M + , where M + = P + (C 6 H 5 ) 3 , P + ( p -FC 6 H 4 ) 3 , N + C 5 H 5 , and S + (CH 3 ) 2 , and several other stable ylides was also investigated.

Synthesis and abnormal reactions of a cholestadienyliron tricarbonyl cation

Abstract Cholesta-1,3-diene- and cholesta-2,4-dieneiron tricarbonyls each react sluggishly with triphenylmethyl tetrafluoroborate to form the same cationic complex. Treatment of the latter with a variety of nucleophiles results in elimination rather than the normally observed addition reaction.

Phthalazine iron carbonyl complexes

Abstract Reaction of phthalazine with diiron enneacarbonyl in benzene at room temperature and with triiron dodecacarbonyl in hot benzene gives mono- and binuclear complexes where the nitrogen atoms behave as two- or three-electron donor ligands. 1,2-Dihydrophthalazine and a binuclear iron carbonyl derivative are formed when the triiron dodecacarbonyl reaction is effected in methanolic benzene.

Sulfur-donor ligand ortho-metalated complexes of ruthenium

Abstract Thiobenzophenones react with triruthenium dodecacarbonyl [Ru 3 (CO) 12 ] in toluene to afford novel sulfur-donor ligand ortho -metalated complexes in high yield.

Azole chemistry VII. The effect of metal complexation on a ring—chain tautomeric equilibrium

Abstract The chromium tricarbonyl group significantly affects the position of an oxazolidine-imino alcohol tautomeric equilibrium.

The carbonyl insertion reaction of sulfur-donor ligand ortho-metalated iron carbonyl complexes

Amines, phosphines, alcohols, and thiocyanate ion are useful reagents for effecting carbonyl insertion of sulfur-donor ligand ortho-metalated iron carbonyl complexes. The apparent intermediate in these reactions has been isolated.