113572-34-2

Upstream product

• 36477-75-5 tungsten pentacarbonyl tetrahydrofuran 
• 83298-09-3 1,1,2-Tris(diphenylphosphino)ethane 
• 16969-72-5 W(CO)5(NH₂Ph) 
• 113572-37-5 {W(CO)5(1,1,2-tris(diphenylphosphino)ethane)} 
• 113572-34-2 {(CO)5W(1,1,2-tris(diphenylphosphino)ethane)} 
• 113572-45-5 {1,1-bis(diphenylphosphino)ethane-P}pentacarbonyltungsten 
• 829-85-6 diphenylphosphane 

Downstream Products

• 113572-37-5 {W(CO)5(1,1,2-tris(diphenylphosphino)ethane)} 
• 113572-34-2 {(CO)5W(1,1,2-tris(diphenylphosphino)ethane)} 

Relevant academic research and scientific papers

Induced acceleration of phosphine exchange in metal carbonyls by pendant groups of coordinated polyphosphines. Two dangling phosphine arms are much better than one

The kinetics and thermodynamics of isomerization of the linkage isomers (OC)5W[η1-PPh2-CH2CH(PPh 2)2] (1) and (OC)5W[η1-PPh2CH(PPh2)CH 2PPh2] (2) in chloroform have been studied by 31P{'H} NMR over the temperature range of 10-55 °C. Conversion of 1 to 2 is exothermic (△H = -12.25 ± 0.1 kJ mol-1) and is accompanied by a large decrease in entropy (△S = -28.2 ± 0.3 J mol-1 K-1). The reaction proceeds much faster than expected [k = (1.18 ± 0.01) × 10-5 s-1] at 25 °C, and its small activation enthalpy (△H? = 92.6 ± 1.9 kJ mol-1) and large negative activation entropy (△S? = -28.2 ± 6.2 J mol-1 K-1) suggest an associative mechanism. The reaction is 4 orders of magnitude faster than the isomerization of (OC)5W[η1-PPh2CH2CH 2P(p-tol)2] (3) to (OC)5W[η1-P(p-tol)2CH2CH 2PPh2] (4). Exchange of coordinated and dangling phosphines is faster than chelation for each of the four complexes, but chelation of 1 or 2 is much faster than chelation of 3 or 4. It appears that the second dangling phosphine arm present in 1 and 2 accelerates the exchange of all metal-attached ligands. Also observed is long-range phosphorus-carbon coupling, possibly enhanced by a through-space interaction, between the short-armed dangling phosphine and the equatorial carbonyl groups (4JPC = 3.89 Hz).

Complexes of 1,1,2-Tris(diphenylphosphino)ethane with Group 6 Metal Carbonyls

The preparation of (Ph2P)2CHCH2PPh2 (tppe) and its reactions with (M=Cr, Mo, or W) are described.In the 1:1 complexes (n=3-5) there are five possible modes of co-ordination, and all have been identified although indirect synthetic