Synthesis of palladium and platinum donor complexes and study of their participation in self-assembly reactions. X-ray crystal structure of [Pt(C6H4CCC5H4N)2(dppp)] (dppp=1,3-bis(diphenylphosphino)propane) (original) (raw)
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Inorganic Chemistry, 1984
The new linear trimetallic complexes tran~-Pt[M(C0)~Cp],(PhCN), [M = Cr (la), Mo (Za), W (3a)l have been isolated and characterized. The isocyanide complexes tram-Pt [ Cr(CO) ,Cp] 2(t-BuNC), (lb) and trans-Pt [ Cr (CO) ,Cp] , [ c-C6H I 'NC] , (IC) have also been prepared because they are related to la. The first reported u(Pt-Cr) frequencies are 173, 174, and 177 cm-I for la-c, respectively. The complex tran~-Pt[Mn(C0),]~(PhCN)~ (4a) has also been synthesized. It reacts with PPh, to give the Pt5(CO)6(PPh,)4 cluster and with CO to afford the linear trimetallic trans-Pt[Mn(CO)S]2(C0)2 (4) complex. The syntheses, characterizations, and X-ray structures of a family of new heterotetrametallic clusters Pt2M2Cp2(C0)6(PR,), [Cp = q5-C5H5; M = Cr (5), Mo (6), W (7); R = Me (e), Et (f), n-Bu (g), Ph (h)] are described. Two different synthetic routes have been shown to lead to these clusters. In method A, the PtC12(PR,), complexes were reacted with 2 equiv of Na[M(CO),Cp] in THF. A complex redox reaction occurs, accompanied by ligand transfer and cluster formation. Thus, the dimers [M(C0)3Cp]2 and/or derivatives thereof such as the new Mo2(CO),(PMe3)Cp, were obtained, together with the mixed-metal clusters in which only one PR3 ligand is coordinated to each Pt atom. Method B involves the reaction in T H F of 1 equiv of phosphine with the linear trimetallic complexes la-3a. Substitution of PhCN for PR, induces a fragmentation of the complex into reactive units that combine with each other, affording the stable compounds. Mechanisms involving radical intermediates are proposed for these reactions. In general, method B presents significant advantages over method A, namely (i) higher cluster yield (up to 87%), (ii) a readily available stable platinum precursor, and (iii) generality and economy of introduction of a phosphine ligand into a cluster molecule. An X-ray diffraction study has been performed on the complexes Pt2M2Cp2(ps-C0)2(p-C0)4(PEt3)2 [M = Cr (5f), Mo (60, W (701. Data for 5f monoclinic, space group R l / c with Z = 2, a = 10.765 (6) A, b = 9.430 (4) A, c = 17.450 (5) A, 0 = 115.37 (2)O, p(ca1cd) = 2.13 g cm-,. For 2321 reflections with I > 3 4 , R = 0.032. Data for 6 f triclinic, space group Pi with Z = 2, a = 10.026 (2) A, b = 11.155 (4) A, c = 15.126 (4) A, a = 85.17 (2)O, j3 = 75.44 (2)O, y = 84.33 (2)O, p(ca1cd) = 2.29 g cm-,. For 4574 reflections with I > 3 4 8 , R = 0.051. There are two slightly different molecules, A and B, in the unit cell. Complex 7f crystallizes in two different monoclinic cells, of P2,/n space group with Z = 2: a = 8.768 (7), 11.920 (2) %.; 6 = 14.147 (2), 12.930 (6) A; c = 13.580 (6), 12.166 (3) A; j3 = 77.96 (5), 61.72 (2)'; p(ca1cd) = 2.60 g cm-,; 2365, 1921 reflections with I > 3 4 8 , R = 0.033,0.085 for types A and B, respectively. All these structures are characterized by a planar, triangulated parallelogram framework for the metallic core. The center of symmetry of these molecules is at the middle of the Pt-Pt' bond. This distance is rather short, ranging from 2.612 (1) (in 5f) to 2.677 (1) %. (in 6f A). The Pt-M distances have values of 2.748 (1) and 2.709 (1) A for M = Cr and range from 2.777 (2) to 2.846 (1) A for M = Mo and from 2.775 (1) to 2.836 (1) A for M = W. A shorter Pt-M distance is found where the contributions of the bridging carbonyls on this bond is higher. In these 58-electron clusters, the 18-electron [CpM(CO),]-fragments bridge the L-+Pt(I)-Pt(I)+L unit in a very original way: a three-legged piano-stool structure with the two Pt atoms located within the M(CO), cone. Each PEt, ligand is coordinated to a Pt atom with a Pt'-Pt-P angle between 169.7 (1) and 177.7 (1)O and an average Pt-P distance of 2.285 A. The planes of the $-Cp ligands are by symmetry parallel to each other and form a dihedral angle between 75.6 and 86.9' with the metallic plane. The carbonyl ligands C(1)0(1) and C(3)0(3) are semibridging the M-Pt' and M-Pt edges, respectively, whereas C(2)0(2) is semi triply bridging the heterotrimetallic face MPtPt'. By symmetry, an identical geometry is found with the carbonyls bridging M'Pt,M'Pt' and M'PtPt'. This bonding situation is compared in the Pt2Cr2, Pt2M02, and Pt2W2 clusters and related to the difference observed between the Pt-M and Pt'-M distances. Spectroscopic, IR, and 'H, 13C('HJ, and 31P[1H) N M R data indicate that all the Pt2M2 clusters presented here have the same basic structures as 5f, 6f, and 7f and that the solid-state structure is retained in solution. 'J(PtPt) values of 775 and 1039 Hz were found for 6g and 7g, respectively. trun~-Pt[M(C0)~Cp]~(PhCN)~. The synthesis and charac-(1) Organometallic Complexes with Metal-Metal Bonds. 19.
Inorganic Chemistry, 1995
The molecular structure of trans-[(NH&Pt@-l-MeC-)2Pd(NH3)] [Pd(NH3)4]0.5(N03)3-3H20 (1) has been determined by X-ray crystallography. The compound crystallizes in the triclinic space group P i (No. 2), with a = 7.476 A, b = 11.373(3) A, c = 16.397(4) A, a = 87.27(2)", , 8 = 85.32(2)", y = 88.74(2)", and Z = 2. The structure was refined to R = 0.034 and R, = 0.038 for 5045 independent reflections. The complex is best described by a square planar coordination of Pd and a square pyramidal one of Pt with the Pd in the apical position (T over square geometry, TSQ). The Pt and Pd atoms are bridged by two nearly coplanar 1-methylcytosinate anions with a Pt-Pd distance of 2.511(1) A. A theoretical analysis, based on EHMO calculations, highlights the nature of the single M-M' bond in d8-d8 dimers of this type (4:3) and points out the correlations with the better known ds-ds dimers (4:4) characterized by two parallel square planar coordination geometries. The M-M' bond order in the latter is close to zero, but not null. Finally, the fate of the M-M' linkage for adding one or two electrons to the above TSQ species is formally analyzed. A correlation is made with the structural data available for dimers with ds-d9 and ds-dIo electron counts [e.g. Pt(I1)-Cu(1I) and Pt(I1)-Hg(I1) species with bridging nucleobases]. While one additional electron weakens the M-M' linkage without destroying the primary TSQ geometry, two extra electrons force the expulsion of the ligand formerly coaxial with the metals (4:2 adducts). The M-M' interaction in the 4:2 adducts is comparable with that proposed for the 4:4 species.
Inorganic Chemistry
Reaction of [(PMe,Ph)PdCl(p-Cl)2PtCl(PMe2Ph)] (I) with 1,2-bis(diphenylphosphino)acetylene yields the heterobimetallic complex [C12Pd(PhzPCrCPPh2)2PtC12] (11). Solution studies using 31P and 19'Pt NMR spectra reveal that 11 exists in an equilibrium of the type 2[C12Pd(Ph2PC=CPPh2)2PtC12] * [C12Pd(Ph2PC=CPPh2),PdClz] + [C12Pt(Ph2PC=CPPh2)2PtC12]. Crystals of I1 [as the bis(ch1oroform) solvate] are monoclinic, space group P2,/n with two formula units in a cell of dimensions u = 14.41 5 (3) A, b = 12.149 (3) A, c = 15.949 (3) A, and 0 = 91.33 (2)O. The bimetallic complex lies about a crystallographic inversion center, and the Pd and Pt atoms are mutually disordered. The structure was solved by the heavy-atom method and refined by full-matrix least-squares calculations with anisotropic thermal parameters; R = 0.033 and R, = (~W A~/~W F ,~) ' /~ = 0.044 for 2407 observed reflections. The unique metal atom has slightly distorted square-planar geometry with mean M-CI = 2.344 ( 2 )
Organometallics, 1986
Supplementary Material Available: Tables of general Cp*TaCl,, 71414-47-6; Cp*TaC13(PMe3), 71414-45-4; Cp*ClzTa-temperature factor expressions for 1 and 8, positional parameters (PhCSCPh), 75522-28-0; Cp*Cl,Ta(PhC=CH), 75522-33-7; for the hydrogen atoms of 8, and least-squares planes for 1 and Cp*ClzTa(MeC=CMe), 75522-31-5; Cp*TaCl4(PMe3), 71414-46-5; 8 (5 pages); a listing of observed and calculated structure factors P h C e P h , 501-65-5; PhC=CH, 536-74-3; MeC=CMe, 503-17-3; for 1 and 8 (26 pages). Ordering information is given on any MesSiCsCSiMe3, 14630-40-1. current masthead page. A Comparative Study of Isostructural Palladium and Platinum Methyl Complexes. The Structures of cis-Dimethylbis(diphenylmethylphosphine)palladium(I I) and cis-Dimethylbis(diphenylmethy1phosphine)platinum (I I
Organometallics, 1996
Reaction of the sodium bis(iminophosphoranyl)alkanide compounds Na[CR′′(PPh 2 dNC 6 H 4 R′-4) 2 ] (1a, R′′) H, R′) CH 3 ; 1b, R′′) H, R′) OCH 3 ; 1c, R′′) CH 3 , R′) CH 3) with M 2 X 4-(PR 3) 2 (M) Pt, Pd; X) Cl, Br; PR 3) PEt 3 , PMe 2 Ph) yields the four-membered metallacycles MX(PR 3){CR′′(PPh 2 dNC 6 H 4 R′-4) 2 } (2a-f, M) Pt; 3a-c, M) Pd), containing the bis-(iminophosphoranyl)alkanide ligand coordinated in a σ-C,σ-N chelating fashion. The molecular structure of 2e (X) Cl, PR 3) PMe 2 Ph, R′′) CH 3 , R′) CH 3) has been determined by X-ray crystallography. The 1,1-bis(iminophosphoranyl)ethanide ligand (1c) in 2e is σ-C,σ-N-chelated toward the square-planar-surrounded Pt, with N coordinated trans to PMe 2 Ph (Pt-N) 2.132(4) Å) and C trans to Cl (Pt-C) 2.116(4) Å), resulting in a puckered M-N-P-C metallacycle and one noncoordinated phosphinimine moiety. In solution the complexes 2 and 3 undergo a dynamic process, involving an intermediate (for 2) or fast (for 3) N,N′ exchange of coordinated and noncoordinated PdN groups. Heating (to 60-80°C) or prolonged stirring of solutions of the kinetically obtained four-membered metallacycles 2 and 3 gives the orthometalated complexes PtX(PR 3){2-C 6 H 4 PPh(NHC 6 H 4 R′-4)CHPPh 2 d NC 6 H 4 R′-4} (4a-d,f) and PdCl(PR 3){2-C 6 H 4 PPh(dNC 6 H 4 Me-4)CHPPh 2 NHC 6 H 4 Me-4} (5a,c). The X-ray crystal structure of 4a (X) Cl, PR 3) PEt 3 , R′) CH 3) has been determined. The new mononuclear orthometalated Pt complexes 4 contain a σ-C,σ-C′ coordinated [2-C 6 H 4-PPh(NHC 6 H 4 R-4′)CR′′PPh 2 dNC 6 H 4 R′-4]-ligand, in which the ortho-H (Ph) has shifted to a bridge position between the two noncoordinating nitrogen atoms. The four-membered platinacycles 2a,b and the orthometalated platinacycles 4a,b react with 1 equiv of HBF 4 or CF 3 COOH to give 6a,b and 7a,b, respectively, by protonation of the noncoordinated PdNC 6 H 4 R′-4 groups only. Addition of CO 2 to 2a,d and 4c,f results in an aza-Wittig reaction, giving PtCl(PR 3){CH(PPh 2 dNC 6 H 4 R′-4)(PPh 2 dO)} (8a,d) and PtX(PR 3){2-C 6 H 4 PPh(dO)-CHPPh 2 NHC 6 H 4 R′-4} (9c,f), respectively, together with aryl isocyanate and bis(aryl)carbodiimide.
Polyhedron, 2009
Two new bis(diphenylphosphino)isopropylphenylamines, (PPh 2 ) 2 N-C 6 H 4 -CH(CH 3 ) 2 , having the isopropyl substituent at the carbon atom 2 (1) or 4 (2), were prepared by the aminolysis of chlorodiphenylphosphine with isopropyl substituted aniline at the ortho-or para-position, respectively, under anaerobic conditions. Oxidation of 1 and 2 with either aqueous hydrogen peroxide, elemental sulfur or grey selenium in thf gave the corresponding oxides, sulfides and selenides (Ph 2 P@E) 2 N-C 6 H 4 -CH(CH 3 ) 2 , where E = O, S or Se, respectively. The palladium and platinum complexes [M{(Ph 2 P) 2 N-C 6 H 4 -CH(CH 3 ) 2 }Cl 2 ] (M = Pd, Pt) and the copper complex [Cu{(Ph 2 P) 2 N-C 6 H 4 -CH(CH 3 ) 2 } 2 ]PF 6 were isolated from the reaction of the bis(phosphino)anilines with MCl 2 (cod) or [Cu(CH 3 CN) 4 ]PF 6 , respectively. The new compounds were characterized by NMR, IR spectroscopy and elemental analysis. Furthermore, the solid-state structures of two representative complexes were determined using single crystal X-ray diffraction analysis. The compounds of palladium (1d) and platinum (1e), both mononuclear complexes, crystallize in the monoclinic P2 1 /c space group. In both compounds the metal ion has a distorted square-planar coordination geometry. The structural properties of complexes 1d and 1e in the solid state are very similar. The palladium complexes were also tested for their catalytic activities in C-C coupling reactions.
Journal of Organometallic Chemistry, 2011
Reactions of [Pt2(μ-Cl)2(C8H12OMe)2] (1) (C8H12OMe = 8-methoxy-cyclooct-4-ene-1-yl) with various anionic chalcogenolate ligands have been investigated. The reaction of 1 with Pb(Spy)2 (HSpy = pyridine-2-thiol) yielded a binuclear complex [Pt2(Spy)2(C8H12OMe)2] (2). A trinuclear complex [Pt3(Spy)4(C8H12OMe)2] (3) was isolated by a reaction between 2 and [Pt(Spy)2]n. The reaction of 1 with HSpy in the presence of NaOMe generated 2 and its demethylated oxo-bridged tetranuclear complex [Pt4(Spy)4(C8H12-O-C8H12)2] (4). Treatment of 1 with ammonium diisopropyldithiophosphate completely replaced C8H12OMe resulting in [Pt(S2P{OPri}2)2] (5), whereas non-rigid 5-membered chelating ligand, Me2NCH2CH2E−, produced mononuclear complexes [Pt(ECH2CH2NMe2)(C8H12OMe)] (E = S (6), Se (7)). These complexes have been characterized by elemental analyses, NMR (1H, 13C{1H}, 195Pt{1H}) and absorption spectroscopy. Molecular structures of 2, 3, 4, 5 and 7 were established by single crystal X-ray diffraction analyses. Thermolysis of 2, 6 and 7 in HDA gave platinum nanoparticles.The reaction of [Pt2(μ-Cl)2(C8H12OMe)2] (C8H12OMe = 8-methoxy-cyclooct-4-ene-1-yl) with anionic chalcogenolate ligands yields a variety of platinum complexes. A unique demethylated oxo-bridged tetranuclear complex [Pt4(Spy)4(C8H12-O-C8H12)2] has been isolated and structurally characterized. Thermolysis of these complexes in HDA gave platinum nanoparticles.► Pt(II) complexes with weak octenyl group and strong chalcogenolate ligand were synthesized and structurally characterized. ► A new oxo-bridged tetranuclear macrocyclic Pt(II) complex [Pt4(Spy)4(C8H12-O-C8H12)2] has been structurally characterized. ► Binuclear Pt(II) complexes with pyridine-2-thiolate ligand exist as two isomeric forms. ► Platinum complexes containing strong Pt–E (E = S or Se) bond after pyrolysis yield platinum nanoparticles rather than PtE.
Dalton Transactions, 2009
The readily available Pt(0) methyl acrylate complex [Pt{CH 2 =CHC(O)OMe}(PPh 3 ) 2 ] (2) allows access to the known, mixed-valence trinuclear cluster [Pt 3 (m-PPh 2 ) 3 Ph(PPh 3 ) 2 ] (3) in 64% yield. Oxidation of 3 with 2 equivalents of I 2 afforded the new trinuclear complex [Pt 3 (m-I) 2 (m-PPh 2 ) 2 I 2 (PPh 3 ) 2 ] (4) whose molecular structure is similar to that of the related compound of empirical formula [Pt 3 (m-I) 2 (m-PPh 2 ) 2 Cl 0.5 I 1.5 (PPh 3 ) 2 ] (5) which has been generated by oxidation of 3 with successively 1 equivalent of I 2 and 1 equivalent of C 6 H 5 ICl 2 . In these complexes, the four halogen atoms lie on the same side of the almost aligned platinum atoms and the nearly square-planar coordination planes of the metal atoms adopt a "japanese screen", chair-like conformation. The reaction of the dinuclear, metal-metal bonded Pt(I)-Pt(I) complex [Pt 2 (m-PPh 2 ) 2 (PPh 3 ) 2 ] with one equivalent of I 2 afforded the Pt(II) complex [Pt 2 (m-PPh 2 ) 2 I 2 (PPh 3 ) 2 ] (6). The molecular structures of complexes 2·CH 2 Cl 2 , [Pt 3 (m-I) 2 (m-PPh 2 ) 2 (I 1.3 Cl 0.7 )(PPh 3 ) 2 ][Pt 3 (m-I) 2 (m-PPh 2 ) 2 (I 1.7 Cl 0.3 )(PPh 3 ) 2 ]·C 6 H 5 Cl·3CH 2 Cl 2 (5A·5B·C 6 H 5 Cl·3CH 2 Cl 2 ) and 6 have been established by single crystal X-ray diffraction studies.
Journal of Organometallic Chemistry, 1994
The complexes cis-[PtH6nPh,)(PPh,)2], crs-[PtH(Sn(C,H,Me-p),)(PPh,),l, cis-[PtH(Sn(C,H,Me-p),XDIOP)], and cis-[PtH(SiPh,XPPh,),] have been prepared, and the crystal structures of cis-[PtH(SnPh,XPPh,),] and cis-[PtH6iPh,XPPh,)21 have been determined. Both of these complexes exhibit distorted square-planar geometry at platinum. In the tin complex, the Pt-P bonds are almost equal in length, but in the silicon complex, the Pt-P bond trans to silicon is significantly longer than that cis to silicon, in accord with the larger trans influence of silyl ligands.