US 12,145,139 B2
Manganese based complexes and uses thereof for homogeneous catalysis
David Milstein, Rehovot (IL); Alex Nerush, Rehovot (IL); Matthias Vogt, Rehovot (IL); Arup Mukherjee, Rehovot (IL); Noel Angel Espinosa-Jalapa, Rehovot (IL); and Subrata Chakraborty, Rehovot (IL)
Assigned to YEDA RESEARCH AND DEVELOPMENT CO. LTD., Rehovot (IL)
Filed by YEDA RESEARCH AND DEVELOPMENT CO. LTD., Rehovot (IL); and Arkadi Nerush, Rishon LeZion (IL)
Filed on Jul. 13, 2023, as Appl. No. 18/351,557.
Application 18/351,557 is a division of application No. 16/076,697, granted, now 11,731,116, previously published as PCT/IL2017/050152, filed on Feb. 8, 2017.
Claims priority of provisional application 62/409,392, filed on Oct. 18, 2016.
Claims priority of application No. 244052 (IL), filed on Feb. 9, 2016.
Prior Publication US 2023/0372915 A1, Nov. 23, 2023
Int. Cl. B01J 31/00 (2006.01); B01J 31/18 (2006.01); B01J 31/24 (2006.01); C07C 249/02 (2006.01); C07B 43/06 (2006.01); C07B 43/08 (2006.01)
CPC B01J 31/181 (2013.01) [B01J 31/2428 (2013.01); C07C 249/02 (2013.01); B01J 2231/348 (2013.01); B01J 2531/72 (2013.01); C07B 43/06 (2013.01); C07B 43/08 (2013.01)] 19 Claims
OG exemplary drawing
 
1. A manganese complex represented by the structure of any of formula VI, VIA, VIB, VIC or their isomer or salt thereof:

OG Complex Work Unit Chemistry
wherein
L1 is (PRaRb), (NRaRb), imine; oxazoline, sulfide (SRa), sulfoxide (S(═O) Ra), heteroaryl containing at least one heteroatom selected from nitrogen and sulfur; (AsRaRb), (SbRaRb) or a N-heterocyclic carbene represented by the structures:

OG Complex Work Unit Chemistry
L2 is (PRaRb), (NRaRb), imine; oxazoline, sulfide (SRa), sulfoxide (S(═O) Ra), heteroaryl containing at least one heteroatom selected from nitrogen and sulfur; (AsRaRb), (SbRaRb) or a N-heterocyclic carbene represented by the structures:

OG Complex Work Unit Chemistry
L3 and L4 are each independently a mono-dentate two-electron donor selected from the group consisting of CO, PRaRbRc, P(ORa)(ORb)(ORc), NO+, AsRaRbRc, SbRaRbRc, NRaRbRc, SRaRb, nitrile (RCN), isonitrile (RNC), N2, PF3, CS, heteroaryl, tetrahydrothiophene, alkene, alkyne or L3 and L4 form together with the Mn a ring;
L5 is absent or a mono-dentate two-electron donor selected from the group consisting of, CO, PRaRbRc, P(ORa)(ORb)(ORc), NO+, NRaRbRc, AsRaRbRc, SbRaRbRc, SRaRb, nitrile (RCN), isonitrile (RNC), N2, PF3, CS, heteroaryl, tetrahydrothiophene, alkene or alkyne;
X is halide, OCOR, OCH2Q, OCOCF3, OSO2R, OSO2CF3, CN, OR, N(R)2 and RS, BF4, B(C6H5)4, B(C6F5)4, B[(C6H4)(CF3)2], PF6 or ClO4;
X′ is H, halide, OCOR, OCH2Q, OCOCF3, OSO2R, OSO2CF3, CN, OR, N(R)2 or RS;
Q is hydrogen, alkyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkylcycloalkyl, alkylaryl, alkylheterocyclyl or alkylheteroaryl;
Y+is a cationic group bearing a single positive charge;
R, RaRb and Rc are each independently H, alkyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkylcycloalkyl, alkylaryl, alkylheterocyclyl or alkylheteroaryl;
Rj, Rk and Rl are each independently H, alkyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkylcycloalkyl, alkylaryl, alkylheterocyclyl or alkylheteroaryl; and
Z is zero, one, two or three substituents wherein each such substituent is independently selected from the group consisting of alkyl, cycloalkyl, aryl, heterocyclyl, heteroaryl, alkylcycloalkyl, alkylaryl, alkylheterocyclyl, alkylheteroaryl, halogen, nitro, amide, ester, cyano, alkoxy, alkylamino, arylamino, an inorganic support and a polymeric moiety.