NOVELTY - Methods (m1) for producing hydrogen from formic acid comprises contacting formic acid either with a complex (c1) comprising a ligand and a metal or metal ion, or with disubstituted-phosphinoamino containing heterocyclyl-metal compounds (II) or (III). The ligand is disubstituted-phosphinoamino containing heterocyclic compounds (I). The ligand is associated with the metal or metal ion.    USE - The methods (m1) and (m2) are useful for producing hydrogen and carbon dioxide which are useful for producing formic acid or a formate (all claimed), where the produced hydrogen and carbon dioxide gas is useful in hydrogen fuel cells.    ADVANTAGE - The methods (m1) and (m2): utilize complexes and (II)-(VI) as catalysts having a turnover number of 500-500000; do not produce or substantially produce carbon monoxide (all claimed) indicating the purity of the regenerated gas; and are performed under base-free conditions.    DETAILED DESCRIPTION - Methods (m1) for producing hydrogen from formic acid comprises contacting formic acid either with a complex (c1) comprising a ligand and a metal or metal ion, or with disubstituted-phosphinoamino containing heterocyclyl-metal compounds of formula (II) or (III). The ligand is disubstituted-phosphinoamino containing heterocyclic compounds of formula (I) or their deprotonated forms. The ligand is associated with the metal or metal ion.    R1-R4=12C alkyl, 12C aryl or 12C aralkyl (all optionally substituted);    Z1=CR6, N or P;    R5,R6=12C alkyl, 12C aryl, 12C aralkyl, amino, alkoxy (all optionally substituted), OH or H; either    T1=N, NR7, CR8 or CR9R10; and    Q1=P or N; or    optionally, T1+Q1=5 or 6 membered heterocyclic ring (optionally substituted with at least one heteroatom), where at least one atom of the heterocyclic ring is substituted with at least one 12C alkyl, 12C aryl or 12C aralkyl (all optionally substituted), and the heterocyclic ring optionally can have an attached fused ring;    R7-R10=12C alkyl, 12C aryl, 12C aralkyl (all optionally substituted) or H;    R5=12C alkyl, 12C aryl, 12C aralkyl (all optionally substituted) or H;    M1=metal or metal ion that is a group 8 metal or metal ion;    L1=neutral or anionic ligand;    n=0-2; and    X1=halo (preferably Cl) or H.    Provided that when T1 and Q1 form a 5 or 6 membered heterocyclic ring, R3 and R4 are not present. INDEPENDENT CLAIMS are also included for:    (1) a composition comprising disubstituted-phosphinoamino containing heterocyclic compounds of formula (IV);    (2) a composition comprising disubstituted-phosphinoamino containing heterocyclyl-metal compounds of formula (V);    (3) a composition comprising disubstituted-phosphinoamino containing heterocyclyl-metal compounds of formula (VI);    (4) a complex (c2) comprising a ligand and a metal or metal ion, where the ligand is (IV) or their deprotonated forms, and the ligand is associated with the metal or metal ion;    (5) methods (m2) producing hydrogen from formic acid comprising contacting formic acid with either (V) or (VI) without provided that conditions, or the complex (c2); and    (6) methods (m3) for producing formic acid or a formate comprising contacting carbon dioxide and hydrogen under increased pressure relative to atmospheric pressure, with the complexes (c1) or (c2).    R1-R4, R11-R14, R11-R14=12C alkyl, 12C aryl or 12C aralkyl (all optionally substituted);    M2=metal or metal ion that is a group 8 metal or metal ion;    Z11-Z13=CR6, N or P; and    R5=12C alkyl, 12C aryl, 12C aralkyl (all optionally substituted) or H.    Provided that: in (IV), when R1-R4 are tert-butyl, R5 is not H and each Z11 is not CH, when R1-R4 are isopropyl, R5 is not phenyl and each Z11 is not N and when R1-R4 are phenyl, R5 is not H and each Z11 is not CH; in (V) when R11-R14 are tert-butyl, R15 is not H and each Z12 is not CH and when R11-R14 are isopropyl, R5 is not phenyl and each Z12 is not N; and in (VI) when R11-R14 are tert-butyl, R5 is not H, each Z13 is not CH and M2 is not Ru, and when R11-R14 are isopropyl, R5 is not phenyl, each Z13 is not N and M2 is not Ir.