55703-22-5

Upstream product

• 25879-01-0 {Et₄N}{(H)tetracarbonyl iron} 
• 639-58-7 triphenyltin chloride 
• 71-91-0 tetraethylammonium bromide 
• 16182-63-1 dipotassium tetracarbonylferrate 

Relevant academic research and scientific papers

Ligand substitution processes on carbonylmetal derivatives. 1. Reaction of tetracarbonylhydridoferrates with phosphines

Ligand substitution processes on KHFe(CO)4 (1) have been demonstrated for the first time by reaction with various phosphines (2 equiv). The reaction times and the nature of the reaction products strongly depend on (i) the nature of the solvent, (ii) the cone angle of the phosphine, and (iii) the reaction conditions. In protic media (e.g. EtOH), phosphines with small cone angles (P(n-Bu)3, PMe2Ph) react with 1 below room temperature to give the newly characterized H2Fe(CO)2(PR3)2 in good yield, whereas phosphines with larger cone angles react only at higher temperature and afford the disubstituted Fe(CO)3(PR3)2 derivatives in quantitative yield. In aprotic medium (THF), phosphines (P(n-Bu)3, PPh3) react only slowly with 1 at room temperature but do so at reflux temperature to yield K2Fe(CO)4 (50%) and bis- or tris-(phosphine)carbonyliron derivatives. The reaction mechanism involves the formation of a monosubstituted K+[HFe(CO)3(PR3)]- derivative with a rate strongly dependent on the Tolman cone angle of the phosphine. In THF, this basic hydrido carbonyl anion reacts with 1 to yield K2Fe(CO)4 and H2Fe(CO)3(PR3). The latter further reacts to give bis- or tris(phosphine)carbonyliron derivatives. In ethanol, the monosubstituted K+[HFe(CO)3(PR3)]- derivative is protonated to give the neutral dihydride H2Fe(CO)3(PR3), which depending on the reaction conditions, is converted either to H2Fe(CO)2(PR3)2 by CO substitution (at low temperature) or to Fe(CO)3(PR3)2 by H2 elimination (at higher temperature). For phosphines exhibiting small cone angles, the disubstituted dihydride may react further with an excess of phosphine to yield the trisubstituted Fe(CO)2(PR3)3 derivative in good yield.

(1-) as a reagent for the synthesis of tin/iron clusters. Partial crystal structure of (NEt4)22>*SnCl4

The reaction of the NEt4(1+) and PPN(1+) (bis(triphenylphosphine)nitrogen(1+)) salts of (1-) with several tin halides has been investigated.Reaction of (NEt4) with ClSnR3 (R = C6H5, p-C6H4(CH3)) and Cl2Sn(C6H5)2 gives the bimetallic species (NEt4) and (PPN), respectively.Reaction of SnCl4 with (PPN) gives the orange trimetallic complex (PPN)22>.Reaction of with SnCl4 in toluene gives the SnCl4 solvate of the corresponding NEt4(1+) salt, an X-ray diffraction study of which has enabled approximate location of the Sn, Fe, and Cl atoms.The Sn atom in the anion is tetrahedrally surrounded by two chlorides and two Fe(CO)4 units with an average Sn-Fe bond distance of 2.58(3) Angstroem.Addition of an excess of the NEt4(1+) salt to SnCl4 gives the red (NEt4)33>, which reverts to (NEt4)22> up on treatment with 1 equivalent of SnCl4.The use of (PPN)22> as a possible precursor for larger nuclearity clusters has been examined.

Tricarbonyl(phosphine)ferrates(2-), Fe(CO)3(PR3)2-, and their derivatives

A two-step synthesis of K2[Fe(CO)3(PR3)] (PR3 = PPh3, PMe2Ph, and PMe3) from the corresponding Fe(CO)4(PR3) has been developed. Treatment of Fe(CO)4(PR3) with a methanolic solution of [Et4N]OH provided the corresponding monohydrides HFe(CO)3(PR3)-. Deprotonation of monohydrides by K[sec-Bu3BH] in refluxing tetrahydrofuran gave 50-70% isolated yields (based on Fe(CO)4(PR3)) of the thermally stable but exceedingly air-sensitive salts K2[Fe(CO)3(PR3)], which were characterized by elemental analysis, infrared spectra, and reactivity patterns. These are the first isolated salts containing (phosphine)-carbonylmetalate dianions and are extremely reactive. They quickly deprotonated acetonitrile to give essentially quantitative yields of HFe(CO)3(PR3)- and reacted with triphenylstannyl chloride to provide Ph3SnFe(CO)3(PR3)-. Ligand exchange reactions of K2[Fe(CO)3(PPh3)] with CO and P(OMe)3 readily occurred at room temperature and gave 80-90% isolated yields of K2[Fe(CO)4] and K2[Fe(CO)3(P(OMe)3)]. The latter salt contains the first isolated (phosphite)carbonylmetalate dianion and was characterized by elemental analyses and infrared spectra as a triphenyltin derivative, (Ph3Sn)Fe(CO)3(P(OMe)3)-. Treatment of [Et4N][HFe(CO)3(PPh3)] with hot ethanol provided low yields (ca. 10%) of the bridging phosphide salt [Et4N][Fe2(CO)6(μ-CO)(μ-PPh 2)]. Full details on the molecular structure of this anion, which has been mentioned previously in the scientific literature (Kyba, E. P.; Davis; R. E.; Clubb, C. N.; Liu, S. T.; Palacios, H. A. O.; McKennis, J. S., Organometallics 1986, 5, 869), are reported for the first time. Crystal data: triclinic, space group P1 (No. 2); a = 11.140 (1) A?, b = 1-3.982 (4) A?, c = 10.161 (3) A?; α = 105.30 (2)°, β = 103.33 (2)°, γ = 77.21 (2)°, V = 1464 (1) A?3; Z = 2; R = 0.034; Rw = 0.039.