Azine Phosphines Research Articles

Chemistry of the azine phosphine ligand Z,E-PPh 2CH 2C(Bu t)=N-N=CMe(C 6H 4NO 2-4): crystal structure of [Mo(CO) 4{PPh 2CH 2C(Bu t)=N-N=CMe(C 6H 4NO 2-4)}

Condensation of Z-PPh 2CH 2C(Bu t)=NNH 2 with 4-nitroacetophenone gave the azine phosphine Z,E-PPh 2CH 2C(Bu t)=N-N=CMe(C 6H 4NO 2-4) ( I). The corresponding phsophine oxide II was prepared by treatment of I with H 2O 2. The phosphine I with [Mo(CO) 4(nbd)] (nbd=norbornadiene) gave [Mo(CO) 4{PPh 2CH 2C(Bu t)=N-N=CMe(C 6H 4NO 2-4)}] ( 1a); the corresponding tungsten 1b and chromium 1c complexes were made similarly. The crystal structure of 1a was determined by X-ray diffraction and showed the presence of a six-membered chelate ring with the bulky 4-nitrophenyl group held close to the metal. Oxidation of 1a with bromine gave the seven-coordinate molybdenum (II) complex 2. Treatment of [PtMe 2(cod)] (cod=cycloocta-1,5-diene) with I at 20°C gave the dimethyl-platinum (II) complex [PtMe 2{PPh 2CH 2C(Bu t)=N-N=CMe(C 6H 4NO 2-4)}] ( 3a) which with MeI gave the iodotrimethylplatinum(IV) complex 4. Treatment of 3a with C≡O opened the chelate ring to give the dimethyl(carbonyl)platinum(II) complex 5 containing a monodentate phosphine ligand. When 3a was heated in toluene solution at 110°C it gave the cyclometallated methylplatinum(II) complex [PtMe{PPh 2CH 2C(Bu t)=N-N=CMe(C 6H 3NO 2-4)}] ( 6). Treatment of 6 with MeI gave the platinum(IV) complex 7. The dichloropalladium(II) complex [PdCl 2{PPh 2CH 2C(Bu t)=N-N=CMe(C 6H 4NO 2-4)}] ( 3b) was prepared by treatment of [PdCl 2(NCPh) 2] with I in CH 2Cl 2. Treatment of [PtCl 2(NCMe) 2] with 2 equiv. of I gave the trans-bis(phosphine) complex 8. When 2 equiv. of I were treated with [PtCl 2(cod)] followed by NH 4PF 6 this gave the salt 9a containing two six-membered chelate rings; the analogous palladium(II) 9b) salt was also prepared. Treatment of 2 equiv. of I with [PtCl 2(cod)] followed by NH 4PF 6 gave the PF 6 salt 10 containing a six-membered chelate ring and a monodentate ligand. When 10 was treated with AgNO 3 followed by NH 4PF 6 this gave the bis-chelate complex 11 containing five- and six-membered chelate rings. Treatment of [IrCl(CO) 2( p-toluidine)] with I gave the cyclometallated iridium(III) hydride complex [IrHClCO{PPh 2CH 2C(Bu t)=N-N=CMe(C 6H 3NO 2-4)}] ( 12). [RuCl 2(PPh 3) 3] with the phosphine I resulted in the Ru(II) complex 13 in which the ortho hydrogens of the 4-nitrophenyl group are agostically interacting with ruthenium. Proton, Phosphorus-31, some carbon-13 NMR and IR data have been obtained. Crystals of 1a are orthorhombic, space group Pna2 1, with a = 1819.3(2), b = 1050.0(1), c = 1614.8(2) pm and Z = 4; final R = 0.0191 for 2616 observed reflections.

Bidentate and terdentate (P-N-S) complexes of a new thioether azine phosphine Z,E-PPh2CH2C(But)=N-N=C(Me)CH2S(C6H4Me-4) with molybdenum, tungsten, or platinum

Treatment of Z-PPh2CH2C(But)=NNH2 with 4-methylphenylthiomethyl methyl ketone gave the thioether azine phosphine Z,E-PPh2CH2C(But)=N-N=C(Me)CH2S(C6H4Me-4) 1, which with H2O2 gave the corresponding phosphine oxide 2. Treatment of 1 with [Mo(CO)3(η6-cht)] or [W(CO)3(NCEt)3] gave the yellow tricarbonyl complexes fac-[M(CO)3{PPh2CH2C(But)=N-N=C(Me)CH2S(C6H4Me-4)}] 3a (Mo) or 3b (W), respectively. Treatment of 1 with [Mo(CO)4(nbd)] gave the pale yellow tetracarbonylmolbdenum(0) complex [Mo(CO)4{PPh2CH2C(But)=N-N=C(Me)CH2S(C6H4Me-4)}] 4, in which the ligand 1 is bidentate through P and N. Oxidation of either 3a or 4 with 1 equivalent of bromine gave the orange neutral seven-coordinate dicarbonylmolybdenum(II) complex [MoBr2(CO)2{PPh2CH2C(But)=N-N=C(Me)CH2S(C6H4Me-4)}] 5, whereas the tungsten complex 3b with 1 equivalent of bromine gave the seven-coordinate tricarbonyltungsten(II) cation [WBr(CO)3{PPh2CH2C(But)=N-N=C(Me)CH2S(C6H4Me-4)}]+ isolated as the PF6 salt 6. Treatment of 1 with [PtCl2(NCMe)2]gave the yellow dichloroplatinum(II) complex [PtCl2{PPh2CH2C(But)=N-N=C(Me)CH2S(C6H4Me-4)}] 7, in which 1 is bidentate through P and N. When 7 was treated with NH4PF6 in methanol it gave the terdentate salt [PtCl{PPh2CH2C(But)=N-N=C(Me)CH2S(C6H4Me-4)}]PF68a. Deprotonation of 7 with NEt3-NaOH gave the orange neutral chloroplatinum(II) complex [PtCl{PPh2-CH2C(But)N-NC(Me)=CHS(C6H4Me-4)}] 9, containing a terdentate ene-hydrazone phosphine ligand. This neutral complex 9 was reprotonated using HBF4 to give the BF4 salt 8b. Treatment of the phosphine 1 with [PtMe2(cod)] gave the white dimethylplatinum(II) complex [PtMe2{PPh2CH2C(But)=N-N=C(Me)CH2S(C6H4Me-4)}] 10, containing the bidentate azine ligand. Treatment of 10 with MeI gave the white platinum(IV) iodide salt fac-[PtMe3{PPh2CH2C(But)=N-N=C(Me)CH2S(C6H4Me-4)}]I 11a in which the azine is terdentate. When 11a was treated with NH4PF6 in MeOH the PF6 salt 11b was obtained. Treatment of 10 with picric acid gave the yellow methylplatinum(II) picrate salt [PtMe{PPh2CH2C(But)=N-N=C(Me)CH2S(C6H4Me-4)}][OC6H2(NO2)3-2,4,6] 12 and methane. Infrared, 31P–[1H], 1H, and some 13C–[1H] NMRdata are given. Keywords: azine phosphine, thioether, metal-carbonyls, platinum.

Cyclometallation of a pentafluorobenzaldehyde azine phosphine via a CF bond fission by irridium(I): crystal structure of [IrCl 2(CO){Ph 2CH 2C(Bu t) = NN = CH(C 6F 4}

Condensation of Z-PPh 2CH 2(Bu t) = NNH 2 ( 1) with pentofluorobenzaldehyde gave the azine phosphine Z, E-PPh 2CH 2C(Bu t)NNCH(C 6 F 5) When 2 was heated in benzene with [IrCl(CO) 2( p-toluidine)], it gave the cyclometallated dichlorocarbonyliridium(III) complex [IrCl 2(CO){PPh 2CH 2C(Bu tNCH(C 6F 4)}] ( 4), the formation of which involved a CF bond fission. Proton, 31P{ 1H}, 13C{ 1H} and 19F NMR data are given. Crystals of 4 are monoclinic, space group P2 1/ c with a = 10.6313(11), b = 16.0243(14), c = 17.968(2) Å, β=100.258(7)° and Z = 4, R 1 = 0.0299 for 6085 observed reflections with I > 2.0 σ( I).

A general method of generating agostic interaction between RuIIand C–H bonds of tert-butyl, methyl, aryl, heterocyclic or alkenyl groups using azine phosphines

Treatment of [RuCl2(PPh3)3]2 with the azine phosphine Z,E-PPh2CH2C(But)N–NC(Me)But3a, derived from MeC(O)But, gave the δ-agostic tert-butyl complex mer,trans-[RuCl2(PPh3){PPh2CH2C(But)N–NC(Me)But}]4a, in which all nine hydrogens of the tert-butyl group are agostically interacting with ruthenium on the NMR time-scale at 20°C. The analogous δ-agostic tert-butyl complex mer,trans-[RuCl2(PPh3){PPh2CH2C(But)N–NC(H)But}]4b was also prepared. Treatment of 2 with the symmetrical azine diphosphine Z,Z-PPh2CH2C(But)N–NC(But)CH2PPh25 gave the δ-agostic tert-butyl complex mer,trans-[RuCl2(PPh3){PPh2CH2C(But)N–NC(But)CH2PPh2}]6, in which one of the PPh2 groups is unco-ordinated. Treatment of 2 with the azine phosphine Z,E-PPh2CH2C(But)N–NC10H167, derived from pinacolone–fenchone mixed azine, gave the δ-agostic methyl complex mer,trans-[RuCl2(PPh3){PPh2CH2C(But)N–NC10H16}]8, in which the methyl group (C10H3) in the 1-position of the fenchone residue interacts with ruthenium (fenchone = 1,3,3-trimethylbicyclo[2.2.1]heptan-2-one). The unsymmetrical camphor azine monophosphine Z,Z-PPh2C10H15N–NC10H169 also gave a similar δ-agostic methyl complex mer,trans-[RuCl2(PPh3){PPh2-C10H15N–NC10H16}]10(camphor = 1,7,7-trimethylbicyclo[2.2.1]heptan-2-one). Treatment of 2 with the azine Z,E-PPh2CH2C(But)N–NCH(C6H4NMe2-4)11a, derived from 4-dimethylaminobenzaldehyde, gave the δ-agostic complex mer,trans-[RuCl2(PPh3){PPh2CH2C(But)N–NCH(C6H4NMe2-4)}]12a, in which the hydrogens in the 2 and 6 positions of the aryl group are agostically interacting with ruthenium. Similarly, the azines 11b and 11c, derived from 4-methoxybenzaldehyde or 4-nitrobenzaldehyde, gave the δ-agostic complexes 12b and 12c, respectively. Treatment of 2 with the azine 13, derived from 1-methylpyrrole-2-carbaldehyde, gave the δ-agostic complex 14, in which the hydrogen in the 3-position of the heterocyclic group is agostically interacting with ruthenium. Treatment of 2 with the azine 15, derived from benzylideneacetone, gave the δ-agostic alkenyl complex 16. Proton, 31P-{1H} and some 13C-{1H} NMR data are given.

Cyclometallation of azine phosphines of type Z,E-PPh2CH2C(But)N–NCHR (R = an aromatic or heterocyclic group) involving X–Y (X = C, N or O; Y = H, I or Br) bond fission by platinum(II)

The phosphino hydrazone Z-PPh2CH2C(But)NNH21 is shown to be a convenient ‘reagent’ for converting aryl or heterocyclic aldehydes into azines which can then be cycloplatinated readily with C–H, C–I, C–Br, N–H or O–H bond fission. Condensation of 1 with benzaldehyde derivatives (RCHO) gave mixed azines of type Z,E-PPh2CH2C(But)N–NCHR [R = Ph 2a, C6H2(OMe)3-3,4,5 2b, C6H4NO2-4 2c, C6H4I-2 2d, C6H4Br-2 2e, C6H4Cl-2 2f or C6H2(OH-2)(OMe)2-4,6 2g]. The azines 2a–2f reacted with [PtMe2(cod)](cod = cycloocta-1,5-diene) at 20 °C to give dimethylplatinum(II) complexes [[graphic omitted]CHR}]3a–3f respectively, containing six-membered chelate rings. Treatment of 2g with [PtMe2(cod)] effected O–H bond fission to give the O-cyclometallated methylplatinum(II) complex [[graphic omitted](OMe)2-4,6]}]4. When the dimethylplatinum(II) complex 3a was heated in toluene at 100 °C, it underwent C–H bond fission with elimination of CH4 to give the cyclometallated methylplatinum(II) complex [[graphic omitted]C6H4)}]5a. Similarly, 3b and 3c were converted into the corresponding cyclometallated methylplatinum(II) complexes 5b and 5c, respectively. The square-planar dimethylplatinum(II) complex 3d in benzene at 20 °C underwent oxidative addition of the C–I bond to give the cyclometallated iododimethylplatinum(IV) complex mer,cis-[[graphic omitted]H4)}]6a. When the bromo-mixed azine complex 3e was heated in benzene at 75 °C for 16 h the cyclometallated bromodimethylplatinum(IV) complex mer,cis-[[graphic omitted]H4)}]6b formed. In contrast the chloro-mixed azine complex 3f underwent the C–H bond fission and not C–Cl bond fission to give the cyclometallated square-planar methylplatinum(II) complex [[graphic omitted]H3Cl-6)}]5d. The methylplatinum(II) complexes 5a and 5d oxidatively added Mel to give the mer,cis-iododimethylplatinum(IV) complexes 6a and 6c, respectely. Treatment of 1 with 2-carbaldehydes of pyrrole, thiophene or furan gave the corresponding phosphines 7a–7c, which with [PtMe2(cod)] at 20 °C gave the dimethylplatinum(II) complexes 8a–8c, respectively. When 8a, derived from the pyrrole azine phosphine, was heated at 50 °C for 10 min, the N-cyclometallated methylplatinum(II) complex [[graphic omitted])}]9 and methane were formed via a N–H bond fission. When the dimethylplatinum(II) complexes 8b or 8c, derived from the thiophene or furan azine phosphines, were heated at 100 °C in toluene they underwent C–H bond fission to give the cyclometallated methylplatinum(II) complexes [[graphic omitted]H2X)}](X = S 10a or O 10b), which oxidatively added Mel to give the iododimethylplatinum(IV) complexes mer,cis-[[graphic omitted]H2X)}](X = S 11a or O 11b), respectively. Proton, 31P-{1H} and some 13C-{1H} NMR data have been obtained.

Terdentate (P,N,N) complexes of a new pyridyl azine phosphine Z,E-PPh2CH2(But)CN–NC(Me)C5H4N and its deprotonated derivative (an azo phosphine) with transition metals

tert-Butyl diphenylphosphinomethyl ketone hydrazone, Z-PPh2CH2C(But)NNH2 condensed with 2–acetylpyridine to give Z,E-PPh2CH2(But)CN–NC(Me)C5H4N la, which reacts with [M(CO)4(nbd)](nbd = norbornadiene) to give highly coloured tricarbonyl complexes [[graphic omitted]}](M = Mo 1a, W 1b or Cr 1c). Under mild conditions, la reacted with [PtMe2(cod)](cod = cycloocta-1,5-diene) to give the dimethylplatinum(II) complex [[graphic omitted]C(Me)C5H4N}]2 containing the bidentate azine phosphine ligand. Complex 2 reacted with Mel to give the fac-trimethylplatinum(IV) iodide salt [[graphic omitted]}]3 in which the phosphine is terdentate. Under slightly acidic conditions, la reacted with [PtMe2(cod)] to give a yellow methylplatinum(II) cation isolated as the PF6 salt, [[graphic omitted]}]PF64a. Deprotonation of this cation with NaOMe gave the deep blue neutral methylplatinum(II) complex [[graphic omitted]}]5a, containing a terdentate azo phosphine ligand. Treatment of [PtCl2(cod)] with la gave the yellow chloride salt [[graphic omitted]}]Cl 4b, which with NH4PF6 gives the corresponding PF6 salt 4c. Sodium methoxide immediately deprotonates 4b to give the intensely deep blue neutral chloroplatinum(II) complex [[graphic omitted]}]5b. Treatment of [PdCl2(NCPh)2] with la gave the yellow chloropalladium(II) chloride salt [[graphic omitted]}]Cl 4d, which on deprotonation with NEt3, gives the deep purple, neutral chloropalladium(II) complex 5c. Infrared, 31P-{1H}, 1H, some 13C-{1H} NMR and UV/VIS data are given.

General strategy for inducing C–H bond fission (cycloiridation) in some aryl, heterocyclic, alkenyl or alkyl groups in azines derived from aldehydes or methyl ketones

The phosphino hydrazone Z-PPh2CH2C(But)NNH2I has been shown to be a convenient ‘reagent’ for converting aldehydes or ketones into azines which can then be cycloiridated rapidly with C–H bond fission to give iridium(III) hydrides. Condensation of I with a series of substituted benzaldehydes (RCHO) gave mixed azines of type Z,E-PPh2CH2C(But)N–NCHR [R = C6H2(OMe)3-3,4,5 IIa, Ph IIb, C6H4OMe-4 IIc, C6H4NO2-4 IId, C6H4Br-2 IIe, C6H4Cl-2 IIf, C6H4F-2 IIg, C6H4OH-2 IIh or C6H2(OH-2)(OMe)2-4,6, IIi]. The Z,E configuration is necessary for the subsequent cyclometallation and when the azine IIa was treated with [IrCl(CO)2(H2NC6H4Me-p)] in benzene at 75 °C for 5 min it underwent an aryl C–H bond fission to give the cyclometallated chlorocarbonyliridium(III) hydride [[graphic omitted]H(OMe)3-3,4,5]}]1a. The crystal structure of 1a showed that (i) oxidative addition of the aryl C–H bond to iridium was cis with the hydride ligand trans to chloride, and (II) the cyclometallated azine ligand was in the terdentate mer arrangement. Azines IIb–IIg reacted similarly. Treatment of IIh with [IrCl(CO)2(H2NC6H4Me-p)] in dichloromethane at 20 °C effected O–H bond fission to give the O-cyclometallated iridium(III) hydride [[graphic omitted])}], which isomerised in benzene at 75 °C to the C-metallated isomer. Similar treatment of IIi also gave an O-cyclometallated iridium(III) hydride. The phosphino hydrazone I condensed with ferrocenecarbaldehyde to give an azine, which with [IrCl(CO)2(H2NC6H4Me-p)] gave a cyclometallated iridium(III) hydride. Treatment of I with the 2-carbaldehydes of pyrrole, N-methylpyrrole or thiophene or with indole-3-carbaldehyde gave the corresponding azine phosphines with the required Z,E configuration. When the pyrrole azine was treated with [IrCl(CO)2(H2NC6H4Me-p)] the N-cyclometallated chlorocarbonyliridium(III) hydride [[graphic omitted])}] was formed via a N–H bond fission. The azine phosphines of N-methylpyrrole, thiophene and indole gave C-cyclometallated chlorocarbonyliridium(III) hydrides. Condensation of I with cinnamaldehyde or 3-methylpent-3-en-2-one gave azines which underwent oxidative addition of the olefinic C–H bonds readily to give corresponding C-cyclometallated iridium(III) hydrides. Phosphino hydrazone I also condensed with tert-butyl methyl ketone to give an azine which with [IrCl(CO)2(H2NC6H4Me-p)] gave the C-cyclometallated chlorocarbonyliridium(III) hydride, i.e. metallation in this case occurred on the single methyl group. Proton, 31P-{1H} and some 13C-{1H} NMR data are given.

A systematic method of promoting an aryl fluoride to coordinate to ruthenium(11)

The phosphino hydrazone Z-PPh 2CH 2C(Bu t)=NNH 2 ( 1) condenses with 2,6-difluorobenzaldehyde to give Z,E-PPh 2CH 2C(Bu t)=NNCH(C 6H 3F 2−2,6) ( 2a), which reacts rapidly with the labile ruthenium(II) complex [RuCl 2(PPh 3) 3] to give mer, trans-[RUCl 2(PPh 3){PPh 2CH 2C(Bu t)=NNCH(C 6H 3F 2−2,6)1 ( 3a). In the 19F{ 1H} NMR spectrum of 3a the fluorines are coupled equally to P B but are not coupled to PB. In the 31P{ 1H} NMR spectrum, PA is coupled equally to both fluorines, i.e. there is a dynamic system with both fluorines coordinated to ruthenium in turn and coupled to P A, 2 J(P AF)=68 Hz. Similar condensations of 1 with other fluorine-substituted benzaldehydes, viz. pentafluorobenzaldehyde, 2-chloro-6-fluorobenzaldehyde, zalluorobenzaldehyde, 2,3-difluorobenzaldehyde, gave mixed azine phosphines. In each case these mixed azine phosphines when treated with [RuCl 2(PPh 3) 3], displaced two triphenylphosphines to give terdentate chelates showing fluorine coordination to ruthenium. Proton, 31P{ 1H} and 19F{ 1H} NMR data are given and discussed.

Cyclometallation of 2-halogenobenzaldehyde mixed azine phosphines of type PPh 2CH 2C( tBu)NNCH(C 6H 4X- 2) (X = I, Br or Cl) involving facile CX bond fission at tungsten(0)

Condensation of Z-PPh 2CH 2C( tBu)NNH 2 with 2-halobenzaldehydes gave mixed azines of the type ZE-PPh 2CH 2C ( tBu)NNCH(C 6H 4X-2) (X = I, 2a; Br, 2b; Cl, 2c; or F, 2e, respectively). 2a, 2b, or 2c reacted with fac-[W(CO) 3(NCEt) 3] to give tungsten(0) complexes [ W(CO) 3(NCEt){PPh 2CH 2C( tBu) NN CH(C 6H 4X-2)}] ( 3a–3c), which rapidly underwent oxidative addition to give seven-coordinate tungsten(II) complexes of the type [ WX(CO) 3{PPh 2CH 2C( tBu)NNCH(C 6H 4)}] ( 4a–4c). The fluoro- mixed azine Ph 2PCH 2C( tBu)NNCH(C 6H 4F-2) ( 2e) with fac-[W(CO) 3(NCEt) 3] gave [ W (CO) 3(NCEt){PPh 2CH 2C( tBu)NN CH(C 6H 4F-2)}] ( 3e) which did not undergo CF oxidative addition, but when treated with CO or CN tBu gave tungsten(0) complexes of the type [ W (CO) 3L{PPh 2CH 2C( tBu)NCH(C 6H 4F-2)}] (L = CO, 5a or CN tBu, 5b). The mixed azine from 2-chloro-6-fluorobenzaldehyde and 1 i.e. PPh 2CH 2C( tBu)NNCH(C 6H 3Cl-2,-F-6) ( 2d) with fac-[W(CO) 3(NCEt) 3] underwent oxidative addition at the CCl bond to give [ WCl(CO) 3{PPh 2CH 2C( tBu) NN CH(C 6H 3F-6)}] ( 4d) via a tungsten(0) complex 3d. Treatment of the aryl-tungsten(II) complex [ WBr(CO) 3{PPh 2CH 2C( tBu)NNCH(C 6H 4)}] ( 4b) with NaBH 4/CO caused aryltungsten bond fission (reductive elimination) and CN reduction to give the benzylhydrazone-phosphine complex [ W(CO) 4{PPh 2CH 2 C( tBu)NN HCH 2Ph}] ( 6) which was also formed by reducing the benzaldehyde mixed azine phosphine tungsten(0) complex [ W(CO) 4{PPh 2CH 2C( tBu)NN CHPh}] ( 8) with NaBH 4.

A general method of promoting agostic interactions (Ruâ†�–Ha–C) using azine phosphines

Treatment of [RuCl2(PPh3)3] with azine phosphines gives complexes showing strong agostic interactions between ruthenium and C–H bonds of tert-butyl, methyl, aryl or alkenyl groups in dynamic systems; for example, all nine hydrogens of a tert-butyl group are agostically interacting with ruthenium on the NMR timescale at 20 °C.

A general method of promoting oxidative addition of C–H bonds to iridium(I) using azine phosphines

Treatment of [IrCl(CO)2(p-toludine)] with azine phosphines of type Z,E-PPh2CH2C(But)N–NC(Q)R, Q = H or Me, R = an organic group, activates aryl, heterocyclic, alkenyl or aliphatic C–H bonds to give cyclometallated iridium(III) hydrides.

Terdentate (P–N–O) complexes formed from Z,E-PPh2CH2C-(But)N–NCH(C6H4OH-2) or Z,E-PPh2CH2C(But)N–NCH-[C6H2(OH-2)(OMe)2-4,6] and nickel, palladium, platinum, rhodium or iridium

Condensation of Z-PPh2CH2C(But)NNH2 with salicylaldehyde or 4,6-dimethoxysalicylaldehyde gave the azine phosphines Z,E-PPh2CH2C(But)N–NCH(C6H4OH-2)1a or Z,E-PPh2CH2C(But)N–NCH[C6H2(OH-2)(OMe)2-4,6]1b, respectively. Treatment of 1a with [PdCl2(cod)](cod = cyclo- octa-1,5-diene) gave the bidentate chelate complex [[graphic omitted]CH(C6H4OH-2)}]3. The phosphine 1a reacts with Na2PdCl4 in the presence of NaO2CMe to give the terdentate chelate complex [[graphic omitted])}]4a Treatment of the latter with Nal or MgMel gave the corresponding iodopalladium(II) complex 4b or the methylpalladium(II) complex 4c, respectively. The analogous methylplatinum(II) complex [[graphic omitted])}]4d was prepared by treating [PtMe2(cod)] with 1a. Fluxional nickel(II) complexes of type [[graphic omitted])}](X = Cl 4e or Br 4f) were also prepared from NiX2·nH2O. When Ni(O2CMe)2·4H2O was treated with two mol equivalents of 1a a paramagnetic octahedral nickel(II) complex [[graphic omitted])}2]5 was formed. Treatment of [PtCl2(cod)] with two mol equivalents of 1a in the presence of NaO2CMe gave a monocationic platinum(II) chloride salt, which with NH4PF6 gave the PF6 salt. Treatment of 1b with [IrCl(CO)2(MeC6H4NH2-p)] or 0.5 equivalents of [Rh2Cl2(CO)4] in the presence of NEt3 gave the square-planar complexes [[graphic omitted](OMe)2-4,6]}](M = Ir 7a or Rh 7b). The carbonyliridium(I) complex 7a underwent oxidative-addition reactions with Mel, allyl chloride, acetyl chloride or propargyl chloride to give the halogenocarbonyliridium(III) complexes [[graphic omitted](OMe)2-4,6]}]8a–8d respectively. In contrast, the reaction of the carbonylrhodium(I) complex 7b with allyl chloride gave the π-allylrhodium(III) complex [[graphic omitted](OMe)2-4,6]}]9. Proton, 31P-{1H} and some 13C-{1H} NMR data have been attained.