F. J. García Alonso

The Reaction of Poly(chlorophosphazene)s with p-Aminophenol − Specific Formation of Aminophosphazenes with Terminal OH Groups and Aryloxyphosphazenes with Terminal NH2 Groups

The outcome of the reaction of the bifunctional reagent p-aminophenol (HO-C6H4-NH2) with the cyclic triphosphazene [N3P3Cl6] is very dependent on the solvent, the temperature, and the proton abstractor. In THF at room temperature with K2CO3 the reaction is very slow and takes place only through the NH2 group to give a mixture of aminophosphazenes, but in refluxing acetone with Cs2CO3 the reaction is fast and occurs through both the NH2 and the OH groups leading to crosslinked products. The analogous reaction with the bis-spirocyclodichlorotriphosphazene [N3P3Cl2(O2C12H8)2] (O2C12H8 = 2,2′-dioxybiphenyl) is also dependent on the conditions, but is more selective. At room temperature in THF with K2CO3 the reaction gives mostly aminophosphazene derivatives, while in refluxing acetone with Cs2CO3 the known aryloxyphosphazene [N3P3(OC6H4NH2)2(O2C12H8)2] (1) is obtained exclusively. Accordingly, the reactions of p-aminophenol with high molecular weight poly(dichlorophosphazene) [NPCl2]n in THF at room temperature in the presence of K2CO3, occur exclusively through the NH2 groups without crosslinking, forming solutions of the aminophosphazene random copolymers {[NPCl2]1−x[NPCl(NHC6H4OH)]x}n (2a) (x 1) that carry terminal OH groups. The reaction of 2a with NH2Bu (Bu = n-butyl) gave the stable and soluble polymers {[NP(NHBu)2]1−x[NP(NHBu)(NHC6H4OH)]x}n (3). Also, in agreement with the cyclic models, the reaction of p-aminophenol with the partially substituted copolymer {[NP(O2C12H8)]0.8[NPCl2]0.2}n occurs only at refluxing temperatures and in the presence of Cs2CO3, producing the poly(aryloxyphosphazene) derivative {[NP(O2C12H8)]0.8[NP(OC6H4NH2)2]0.2}n (4) possessing terminal NH2 groups, or, if the chlorine substitution is completed with phenol, the analogous polymer {[NP(O2C12H8)]0.8[NP(OC6H5)(OC6H4NH2)]0.2}n (5). (© Wiley-VCH Verlag GmbH, 1 Weinheim, Germany, 2002)

Synthesis of mer-tricarbonyls of manganese(I) with N-donor chelate ligands

Abstract The first mer -tricarbonyl complexes of manganese(I) with N -donor chelate ligands, namely mer -[Mn(CO) 3 (CNR)(NN)]ClO 4 , where CNR = CNBu t , NN = 1,10-phenantroline (phen) or 2,2′-bipyridine (bipy), have been obtained from the reactions of fac -[Mn(CO) 3 (Me 2 CO)(NN)]ClO 4 with isocyanides, CNR. Other members of the [Mn(CO) 4- n (CNR) n (NN)]ClO 4 ( n = 1,2,3,4) series have also been synthesized: viz., fac -[Mn(CO) 3 (CNR)(NN)]ClO 4 (Ia-d) and cis,cis -[Mn(CO) 2 (CNR) 2 (NN)]ClO 4 (CNR = CNBu t , CNPh) (IIa-d), cis,cis -)[Mn(CO) 2 (CNR)(CNR′)(NN)]ClO 4 (CNR = CNPh, CNR′ = CNBu t and CNR = CNBu t , CNR′ = CNPh) (IIe-f), fac -[Mn(CO)(CNBu t ) 3 (NN)]ClO 4 , (IVa-b), and [Mn(CNPh) 4 (NN)]ClO 4 ; (NN) represents phen or bipy. (See Scheme 1 and Table 1).

Synthesis of the first phosphazene random copolymers containing thiophenoxy groups

The reaction of [NPCl2]n with substoichiometric amounts of the thiophenols HS―C 6 H 4 -R (R = H, Br) and Cs 2 CO 3 in THF at room temperature, gave solutions of {[NPCl 2 ] 1-x [NP(S-C 6 H 4 -R)2]}n [ R = H (1a), Br (1b)]. The reaction of the derivative with R = Br and x = 0.3 with HO-C-H 4 -Br gave the random copolymer {NP(O-C 6 H 4 -Br)2] 0.7 [NP(S-C 6 H 4 -Br) 2 ] 0.3 } n (2); similarly, the reaction of 1 with the biphenol HO―C 6 H 4 -C 6 H 4 -OH gave the copolymers {NP(O 2C12 -H 8 )] 0.75 NP(S-C 6 H 4 -R) 2 ] 0.25 } n [R = H, (3a); R = Br, (3B)] as soluble and stable white solids.

Synthese und kristallstruktur von heterometallzweikernkomplexen mit vinyliden-brückenliganden

Abstract The complex C 5 H 5 (PPr 3 i )RhCCH 2 reacts with C 6 H 6 Cr(CO) 3 upon UV irradiation, and with C 5 H 5 Mn(CO) 2 THF and Fe 2 (CO) 9 at room temperature, to give the heterometallic dinuclear complexes C 5 H 5 (PPr 3 i )Rh(μ-CCH 2 )(μ-CO)ML (III: ML = Cr(CO)C 6 H 6 ; V, ML = Mn(CO)C 5 H 5 ; VI: ML = Fe(CO) 3 ). The crystal structures of V and VI have been determined.

Isomerization of cationic carbonyls of manganese(I) with N-donor chelate ligands promoted by reduction

Abstract The carbonyls cis,cis -[Mn(CO) 2 (CN-t-Bu) 2 (NN)]ClO 4 and fac -[Mn(CO)(CN-t-Bu) 3 (NN)]ClO 4 , (NN = 2,2′-bipyridine, bpy, and 1,10-phenantroline, phen), are isomerized to cis,trans - and mer -complexes respectively by reduction in acetonitrile with sodium amalgam and subsequent oxidation by air. The structure of fac -[Mn(CO)(CN-t-Bu) 3 (bpy)]ClO 4 has been determined by X-ray diffraction.

Facile deprotonation of the hydrogensulfido ligand in [Mn2(µ-H)(µ-SH)(CO)6(diphosphine)] complexes

The unsaturated dihydrides [Mn2(µ-H)2(CO)6(µ-L–L)][L–L = Ph2PCH2PPh2(dppm)1; or (EtO)2POP(OEt)2(tedip)2] react with sulfur to yield the hydrogensulfido complexes [Mn2(µ-H)(µ-SH)(CO)6(µ-L–L)](L–L = dppm 3a; or tedip 3b). The hydrogen bound to the sulfur atom in 3a is easily removed by thallium(I) acetylacetonate, generating a species which affords, upon reaction with the appropriate electrophiles, the thiolato complexes [Mn2(µ-H)(µ-SZ)(CO)6(µ-dppm)](Z = Me 3c, SnMe33d, or AuPPh33e). The solid-state structure of 3e has been determined by X-ray methods [monoclinic, space group P21/n, a= 18.840(4), b= 13.024(2), c= 20.243(4)A, β= 108.66(2)°, Z= 4].

SYNTHESIS, SPECTROSCOPIC AND ELECTROCHEMICAL STUDY OF CATIONIC CICLOPENTADIENYLIRON(DIPHOSPHINE) COMPLEXES SUPPORTED ON A HIGH MOLECULAR WEIGHT PHOSPHAZENE POLYMER THROUGH NITRILE LIGANDS

The high molecular weight phosphazene random copolymer {[NP(OC6H5)2]0.94 [NP(OC6H5)(OC6H4CNFe(dppe)Cp)]0.06[PF6]0.06}n (1), that carries [Fe(dppe)Cp] cationic fragments coordinated to nitrile side groups, has been synthesized from the copolymer {[NP(OC6H5)2]0.94[NP(OC6H5)(OC6H4CN)]0.06}n and the complex [Fe(CH3CN)(dppe)Cp][PF6] by the complete elimination of the acetonitrile from the equilibrium mixture that they form in dichloromethane solution. The new polymer has been fully characterized by a detailed discussion of the IR and NMR data that may be also useful for the study of other polymeric complexes with similar metal fragments. The cyclic voltammogram of (1) showed an oxidation process that is chemically irreversible but, rather unexpectedly, electrochemically reversible. All the results were interpreted by comparison with the data obtained for the new cyclic model complexes {N3P3(OC6H4-R)5[OC6H4CNFe(dppe)Cp]}[PF6] R=H (2a), But (2b), (see chart 1) that were synthesized by a similar method using the nitrile phosphazene ligands [N3P3(OC6H4-R)5(OC6H4CN)]

Unexpected formation of hydrido-hydroxy derivatives as direct products in the reactions of the unsaturated dihydrides [Mn2(μ-H)2(CO)6(μ-LL)] (LL = Ph2PCH2PPh2, (EtO)2POP(OEt)2) with carbon dioxide

Abstract The unsaturated dihydrides [Mn2(μ-H)2(CO)6(μ-LL)] (LL = Ph2PCH2PPh2, dppm, 1; (EtO)2POP(OEt)2, tedip, 2) react with carbon dioxide (at 50 atm) or with formic acid to yield not only the expected hydridoformate complexes [Mn2(μ-H)(μ-O2CH)(CO)6(μ-LL)] (LL = dppm, 3a; tedip, 3b but also the hydridohydroxo-derivatives [Mn2(μ-H)(μ-OH)(CO)6(μ-LL)] (LL = dppm, 4a; tedip, 4b. The complexes 4 do not seem to arise from decomposition of 3 or to be products of the reaction of 1 and 2 with water. The hydrides 1 and 2 also react under mild conditions with several heterocumulenes (cyclohexylisocyanate, dicyclohexylcarbodiimide and trimethylsilylazide) to afford [Mn2(μ-H){μ-OC(H)NCy}(CO)6Iμ-tedip)] (5), [Mn2(μ-H{μ-CyNC(H)NCy}(CO)6(μ-LL)] (LL = dppm, 6a; tedip 6b and [Mn2(μ-H)(μ-N3)(CO)6(μ-LL)] (LL = dppm, 7a: tedip, 7b), respectively.

Isocyanide migration from an axial to an equatorial position in the synthesis of octahedral cationic carbonyl complexes of manganese(I) containing nitrogen donor chelate ligands

Abstract Several manganese carbonyl complexes of the type [Mn(CO)m(CNtBu)n(L)p(LL)]ClO4 (m + n + p = 4; m = 1−3; n = 1−3; p = 0, 1; L = P(OMe)3, CNPh; LL = 2,2′-bipiridine (bipy), 1,10-phenantroline (phen), bis(t-butyl)-1,4-diazabuta-2,3-diene (tBu-DAB), N,N,N′,N′-tetramethylethylendiamine (tmed)) have been prepared starting either from fac-[Mn(CO)3(CNtBu)(LL)]ClO4 or fac-[Mn(CO)3{P-(OMe)3}(LL)]ClO4 and using ONMe3 as decarbonylating agent. The stereochemistry of the substitution reactions products is discussed in terms of the nature of the possible intermediates.

Konkurrierende bildung von heterometall-zweikern-komplexen mit μ-CCHPh und μ-ηPsu1,η3-CHCPhCO-brückenliganden bei der reaktion von C5H5Rh(PhCCH)PPri3 MIT Fe2(CO)9

Abstract The alkyne complex C5H5Rh(PhCCH)PPri3 reacts wit Fe2(CO)9 to form two isomeric dinuclear products, C5H5(PPri3)Rh(μ-CCHPh)(μ-CO)Fe(CO)3 and C5H5(PPri3)Rh(μ-η1,η3-CHCPhCO)Fe(CO)3. The X-ray crystal structure of the latter has been determined.