US 12,441,669 B2
PCNHCP metal complexes and uses thereof
Graham De Ruiter, Haifa (IL); and Subhash Garhwal, Haifa (IL)
Assigned to Technion Research & Development Foundation Ltd., Haifa (IL)
Appl. No. 18/042,752
Filed by Technion Research & Development Foundation Ltd., Haifa (IL)
PCT Filed Aug. 22, 2021, PCT No. PCT/IL2021/051024
§ 371(c)(1), (2) Date Feb. 23, 2023,
PCT Pub. No. WO2022/043993, PCT Pub. Date Mar. 3, 2022.
Claims priority of provisional application 63/181,562, filed on Apr. 29, 2021.
Claims priority of provisional application 63/069,395, filed on Aug. 24, 2020.
Prior Publication US 2023/0322647 A1, Oct. 12, 2023
Int. Cl. C07C 5/25 (2006.01); B01J 31/12 (2006.01); B01J 31/22 (2006.01); B01J 31/24 (2006.01); C07B 59/00 (2006.01); C07F 15/02 (2006.01)
CPC C07C 5/2575 (2013.01) [B01J 31/121 (2013.01); B01J 31/2273 (2013.01); B01J 31/2452 (2013.01); C07B 59/00 (2013.01); C07F 15/02 (2013.01); B01J 2231/32 (2013.01); B01J 2231/42 (2013.01); B01J 2531/0244 (2013.01); B01J 2531/842 (2013.01); C07B 2200/05 (2013.01); C07C 2523/745 (2013.01)] 35 Claims
 
1. A metal complex of formula I:

OG Complex Work Unit Chemistry
wherein:
R1, R2, R3, and R4 each independently is selected from the group consisting of (C1-C18)alkyl, (C2-C18)alkenyl, (C3-C7)cycloalkyl, —O—(C1-C18)alkyl, (C3-C12)heterocyclyl, a 6-14-membered aryl, and a 5-10-membered heteroaryl; or R1 and R2, and/or R3 and R4, together with the phosphorus atom to which they are attached form a heterocyclic ring optionally containing one or more heteroatoms selected from the group consisting of O, N, and S;
R5, R6, R7, R8, R9, and R10 each independently is selected from the group consisting of H, (C1-C18)alkyl, (C2-C18)alkenyl, (C3-C7)cycloalkyl, (C3-C12)heterocyclyl, a 6-14-membered aryl, a 5-10-membered heteroaryl, —CF3, —OR, —SR, and —NRR′, or any two of adjacent R5, R6, R7, R8, R9, and R10 together with the carbon atoms to which they are attached form a 5-14-membered ring optionally containing one or more heteroatoms selected from the group consisting of O, N, and S;
M is an earth-abundant metal having an oxidation state selected from the group consisting of −2, −1, 0, +1, +2, +3, +4, +5, and +6;
X, Y and Z each independently is selected from the group consisting of H, deuterium (D), tritium (T), N2, CO, NO, N2O, (C1-C18)alkyl, (C2-C18)alkenyl, (C3-C7)cycloalkyl, —O—(C1-C18)alkyl, (C3-C12)heterocyclyl, a 6-14-membered aryl, a 5-10-membered heteroaryl, halogen, azide (N3−), cyanide (CN−), cyanate (OCN−), isocyanide (RNC), isocyanate (RNCO), thiocyanate (SCN−), isothiocyanate (RNCS), sulfide (S2−), oxo (O2−), peroxo (R—O—O), hydroperoxo (H—O—O−), superoxide (O2−), —NRR′, —SR, and a coordinating solvent; or one of X, Y and Z is selected from the group consisting of H, D and T, and the other two of X, Y and Z form a bidentate ligand;
R and R′ each independently is selected from the group consisting of H, (C1-C18)alkyl, (C2-C18)alkenyl, (C3-C7)cycloalkyl, (C3-C12)heterocyclyl, a 6-14-membered aryl, a 5-10-membered heteroaryl, and a trialkylsilyl;
Q is an optional counter ion; and
the asterisk represents an optional net charge of said metal complex which depends on the oxidation state of said metal and the groups X, Y and Z,
provided that at least one of X, Y and Z each independently is selected from the group consisting of H, D, and T.