Transition metal complexes with bidentate ligands spanning trans-positions. VI. The preparation of some diaryl- and dialkyl derivatives of 2,11-bis (phosphinomethyl)benzo [c]phenanthrene

The preparation of the ditertiary phosphines 2,11-bis (di-m-tolylphosphinomethyl)benzo [c]phenanthrene ( 1b ), 2,11-bis (di-p-anisylphosphinomethyl)benzo-[c]phenanthrene ( 1c ), 2,11-bis (di-m-trifluoromethylphenylphosphinomethyl) benzo-[c]phenanthrene ( 1d ), 2,11-bis (dicyclohexylphosphinomethyl)benzo [c]phenanthrene ( 1e ) and 2,11-bis [di-(t-butyl)phosphinomethyl]benzo [c]phenanthrene ( 1f ), by a combination of synthetic routes is described.     

Transition-Metal Complexes with Bidentate Ligands Spanning trans-Positions. Part XVII. Some platinum(II) complexes with anionic ligands such as methoxide,formate, carboxylate,hydride, and borohydride,and the X-ray crystal structure of [PtHCl( )] (PP = 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene)

The complexes trans-[PtXY( 2 ] (X = H or Me; Y = OMe, OCHO, CO₂H, and BH₄; 2 = 2,11-bis{bis[3-(trifluoromethyl)phenyl]phosphinomethyl}benzo[c]phenanthrene) were prepared, and their decompositions to trans[PtHX( 2 )] were studied. Some binuclear hydrido-bridged complexes, e.g.[( 2 )HPt(μ-H)PtH( 2 )]⁺, were also obtained. The preparation of complexes trans-[PtHX( 28 )₂] (X = H or Me, 28 = bis[3-(trifluoromethyl)phenyl]benzylphosphine) is also reported. The X-ray crystal structure of trans-[PtHCl 1 )] ( 1 = 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene) was carried out.     

Transition-Metal Complexes with Bidentate Ligands Spanning trans-Positions. II. Preparation and properties of complexes trans-[MX2(1)] (M = Ni,Pd and Pt; X = Cl,Br and I; 1 = 2, 11-Bis(diphenylphosphinomethyl)benzo[c]phenanthrene)

It is shown that the ligand 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene ( 1 ) reacts with nickel(II), palladium(II) and platinum(II) substrates giving either exclusively, or predominantly, mononuclear complexes of the type trans-[MX₂( 1 )] in which the organic ligand spans trans-positions. It is further shown that the spectroscopic properties which are mainly associated with metal and donor atoms in complexes of this type are closely related to those of the corresponding square planar complexes of the type trans-[MX₂(Ph₂PCH₂Ph)₂].     

Transition Metal Complexes with Bidentate Ligands Spanning trans-Positions. VII. The preparation of the five-coordinate complexes [M(CO)3(1)] (M = Fe,Ru; (1) = 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene)

The five-coordinate mononuclear complexes [M(CO)₃( 1 )] (M = Fe, Ru; ( 1 ) = 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene) have been prepared and assigned trigonal bipyramidal structures with apical phosphorus atoms from IR. and NMR. data.     

Transition-Metal Complexes with Bidentate Ligands Spanning trans-Positions. III. Preparation and solution studies of complexes [MX(1)] (M = Cu,Ag and Au; X = anionic ligand; 1 = 2, 11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene)

The preparation of monomeric complexes [MX( 1 )] is reported where M = Cu, Ag, Au; X = I, Cl, NO₃, BF₄ and 1 = 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene. The solution structure of the complexes is discussed on the basis of molecular weight, conductivity and NMR. measurements. In acetonitrile and nitromethane, the nitrate and fluoroborate complexes exist as ionic species [M( 1 )]⁺X^? whereas the halo-complexes are present as equilibrium mixtures of ‘covalent’ and ‘ionic’ forms. All the complexes are associated in CH₂Cl₂-solutions. The values of ¹J show that this association in [Ag(NO₃) ( 1 )] and [Ag(BF₄) ( 1 )] is best described in terms of ion-pairing while that for species [AgX( 1 )] (X = Cl, Br and I) is mainly ‘covalent’ in nature. Evidence is presented for the formation of the complex ion [Ag(CH₃CN)_n( 1 )]⁺ in acetonitrile solution.     

Transition-Metal Complexes with Bidentate Ligands Spanning trans-Positions. IX. Preparation and 1H-NMR. Studies of complexes [MX2(1)] and [M′Cl(CO)(1)] (M = Pd,Pt; M′ = Rh,Ir; X = Cl,Br, I; 1 = 2, 11-Bis-(diphenylarsinomethyl)benzo[c]phenanthrene) and crystal and molecular structure of [PtCl2(1)]

The preparation of the bidentate ligand 2, 11-bis(diphenylarsinomethyl)benzo-[c]-phenanthrene ( 1 ) is described. This ligand reacts with appropriate substrates to give mononuclear square planar complexes of type [MX₂( 1 )] (M = Pd, Pt; X = Cl, Br, I) and [M′Cl(CO)( 1 )] (M′ = Rh, Ir) in which ligand 1 spans trans-positions. This is confirmed by the crystal structure of [PtCl₂( 1 )]. ¹H-NMR. spectra of the complexes are discussed and compared with those of model compounds trans-[MCl₂( 12 )₂] (M = Pd, Pt) and [M'Cl(CO)( 12 )₂] (M′ = Rh, Ir; 12 = AsBzPh₂).     

Transition-metal complexes with bidentate ligands spanning trans-positions. V. Crystal and molecular structures of complexes [RhCl(CO) (1)] and [PdCl2(1)]; 1 = 2,11-bis (diphenylphosphinomethyl)benzo [c]phenanthrene

The structures of [RhCl(CO) ( 1 )] and [PdCl₂ ( 1 )], where 1 is the bidentate ligand (C₆H₅)₂P·CH₂·C₁₈H₁₀· CH₂·P(C₆H₅)₂, have been determined from threedimensional X-ray counter data collected on single crystals of the C₆H₅·CN solvates. The two compounds are isomorphous and crystallize in the triclinic system, space group P 1 , Z = 2: a = 14.580 (8), b = 13.029 (10), c = 11.909 (6) Å, α = 106.33 (5), β = 100.47 (4), γ = 95.73 (5)° for the rhodium complex; a = 14.361 (5), b = 13.044 (7), c = 11.897 (4) Å, α = 105.97 (4), β = 100.27 (3), γ = 94.76 (4)°, for the palladium complex. In both complexes the metal atom is four-coordinate with slightly distorted square-planar configuration. In both cases the ligand 1 spans trans positions with M-P bond lengths in the ranges of the literature data. Also the other bond distances fall in regular ranges. Ligand 1 has almost the same conformation in both complexes and is characterized by a strong out-of-plane deformation of the benzophenanthrene system as a consequence of severe overcrowding.     

Synthesis and Characterization of Three New Zipper‐like Lanthanide [Ln = TmIII,NdIII, CeIII] Coordination Polymers Containing 1,3‐Benzenedicarboxylate and 2‐Phenyl‐1H‐1,3,7,8‐tetraazacyclopenta[l]phenanthrene Ligands

Reaction of the ligands 2‐phenyl‐1H‐1,3,7,8‐tetraazacyclopenta[l]phenanthrene (PTCP) and benzene‐1,3‐dicarboxylic acid (m‐H₂BDC) with Ln₂O₃ under hydrothermal conditions lead to three isomorphous coordination polymers [Ln₂(PTCP)₂(m‐BDC)₃·H₂O]_n (Ln = Tm, 1 ; Nd, 2 ; Ce, 3 ). The coordination polymers crystallize in monoclinic, space group P2₁/m with a = 9.8340(2), b = 17.9140(4), c = 15.6050(3) Å, β = 100.51(3)° for 1 , with a = 9.8423(3), b = 18.3562(4), c = 15.6209(3) Å, β = 102.138(3)° for 2 , and with a = 9.8620(2), b = 18.4960(4), c = 15.6530(3) Å, β = 102.42(3)° for 3 , respectively. The metal ions (Ln³⁺) are located in an octacoordinated environment and the dinuclear [Ln₂O₁₂N₄] units act as octahedral secondary building units (SBU), which are bridged in two coordination modes by six m‐BDC ligands to form a three‐strand‐like chain. These chains are decorated by PTCP ligands and form unique three zipper‐like structures, which are further assembled into three‐dimensional supramolecular nets by π ··· π stacking interactions. Additionally, hydrogen bonds are observed in the structures. Furthermore, compounds 1 – 3 were studied by IR spectrocopy and thermogravimetric analyses.     

Transition-Metal Complexes with Bidentate Ligands Spanning trans-Positions. I. The synthesis of 2,11-bis(diphenylphosphinomethyl)benzo[c]-phenanthrene,a ligand promoting the formation of square planar complexes

The bidentate ligand 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene ( 1 ) was synthesized from 2,11-dimethyl-benzo[c]phenanthrene ( 3 ) via the corresponding bromomethyl derivative 9. 3 was obtained from the cyclization with boron trifluoride etherate of 1,1-di-(p-methylphenethyl)-epoxyethane ( 7 ), which was prepared from 1,5-di(p-tolyl)-pentan-3-one ( 6 ).     

Kristallstrukturen „supramolekularer”︁ (Benzo‐18‐krone‐6)kaliumtetrathiocyanatometallate: Ein dimerer Komplex {[K(Benzo‐18‐krone‐6)]2[Hg(SCN)4]}2 und zwei isomere Komplexe [K(Benzo‐18‐krone‐6)][Cd(SCN)3] mit kettenförmigen Trithiocyanatocadmat‐Anionen

Crystal Structures of „Supramolecular”︁ Benzo‐18‐crown‐6 Potassium Tetrathiocyanato Metallates: A Dimeric Complex {[K(Benzo‐18‐crown‐6)]₂[Hg(SCN)₄]}₂ and Two Isomeric Complexes [K(Benzo‐18‐crown‐6)][Cd(SCN)₃] Containing Trithiocyanato Cadmate Anions with Chain Structures By reaction of potassium thiocyanatomercurate(II) complexes with benzo‐18‐crown‐6 (2,3‐benzo‐1,4,7,10,13,16‐hexaoxacyclooctadec‐2‐ene) crystals of {[K(benzo‐18‐crown‐6)]₂[Hg(SCN₄)]}₂ ( 1 ) were obtained. 1 crystallizes monoclinic, space group P2₁/n (non‐standard setting of P2₁/c), a = 1737.35(2), b = 1377.16(2), c = 1984.12(3) pm, β = 100.637(1)°, Z = 2. With potassium tetrathiocyanatocadmate(II) two modifications of a complex [K(benzo‐18‐crown‐6)][Cd(SCN)₃] ( 2 , 3 ), of different symmetry were formed. 2 crystallizes monoclinic, P2₁/c, a = 1158,31(3), b = 1096,55(2), c = 2028,46(2) pm, β = 99,5261(2)°, Z = 4, 3  orthorhombic, P2₁cn, a = 1105,95(3), b = 1413,07(4), c = 1617,10(5) pm, Z = 4. 1 has a dimeric structure, built up from a dication K₂(benzo‐18‐crown‐6)₂]²⁺ and two [K(benzo‐18‐crown‐6)]⁺ cations, which are bridged by two [Hg(SCN)₄]^2– anions. In 2 and 3 triply bridged infinite [{Cd(SCN)₃^–}_n] zigzag chains, stretching along screw axes, are to be found as anions. In 2 these chains exist in two conformations related by inversion symmetry, whereas in 3 only one form can be found. [K(benzo‐18‐crown‐6)]⁺ cations are linked to the anion chains via K · · · S interactions of different lengths.     

Transition Metal Complexes with Bidentate Ligands Spanning trans-Positions. Part XIII. Preparation,properties and crystal and molecular structures of chlorocarbonyl-2,11-bis(diphenylphosphinophenyl) benzo[c]phenanthreneiridium (I) and trichlorocarbonyl-2,11-bis(diphenylphosphinomethyl) benzo[c]phenanthreneiridium(III)

The complex [IrCl₃(CO)( 1 )]( 4,1 =2,11-bis (diphenylphosphinomethyl)benzo[c]phenanthrene) has been prepared by CuCl₂-oxidation of [IrCl(CO)( 1 )]( 2a ). It is shown that the chlorine oxidation of 2a gives a mixture of products whose composition depends on the reaction conditions. The X-ray crystal structures of 2a and 4 have been determined. The small conformational differences observed for the trans-spanning ligand 1 in the two complexes are likely to be caused by the difference in Ir-P bond lengths in square planar 2a and octahedral 4 (2.310(4) and 2.411(3) Å, respectively).     

Transition metal complexes with bidentate ligands spanning trans-positions part XV X-ray structural and 31P-NMR solution studies of some three-coordinate silver complexes of 2,11-bis[di(tert-butyl)phosphinomethyl]benzo[c]phenathrene and related ligands

A series of three-coordinate bis(dialkylphosphinomethyl)benzo[c]phenanthrene Ag(I) complexes, alkyl= t-Bu, (1b) , and cyclohexyl, (1c) , anion = BF₄, CIO₄, CIO₄, NO₃, Cl, Br, I, have been prepared and thier ³¹ P-NMR characteristics recorded. The solid state structures of [Ag( 1b )Br], [Ag( 1b )Cl] and [Ag( 1b )CIO₄] have been determined by X-ray diffraction. The Ag atom in these complexes shows distorted trigonal geometry. Selected bond lengths and angles are as follows: Ag-P = 2.463(4) Å and 2.433(5) Å, P-Ag-P=141.6(2)° in the bromo complex, Ag-P = 2.457(2) Å and 2.427(2) Å, P-Ag-P = 142.6(1)° ion the chloro complex, and Ag-P = 2.394(2) and 2.393 (2) Å, P-AG-P = 161.5(1)° in the perchlorato complex.     

Overcrowded molecules. V. 3,10-dimethyl-1,12-bis(2-pyridyl)benzo[c] phenanthrene-2,11-diol

The bis ketene acetal adduct of 4a,10a-diazoniaanthra[1,2-α]anthracene diperchlorate ( 10 ) was used to prepare the highly overcrowded benzo[c]phenanthrene 2 by a known procedure. Its oxidation with cupric chloride provided the isoxazolium zwitterion, 3 , via an intramolecular cyclization.     

The synthesis of novel polycyclic heterocyclic ring systems via photocyclization. 2 . Benzo[h][1]benzothieno[2,3-c]quinoline and benzo[h][1]benzothieno[2,3-c]quinoline

The synthesis of two previously unknown unsubstituted heterocyclic ring systems namely, benzo[h][1]benzothieno[2,3-c]quinoline ( 6 ) and benzo[f][1]benzothieno[2,3-c]quinoline ( 12 ) is reported. These two novel ring systems have been assembled by photocyclization of the appropriate amides.     

The syntheses of 4b,5a-dihydro-5H-benzo[3,4]-phenanthro[1,2-b]azirine and 1a,11b-dihydro-6,11-dimethyl-1H-benz[3,4]anthra[1,2-b]azirine

The syntheses of the K-imine derivatives of carcinogenic benzo[c]phenanthrene and 7,12-dimethylbenz-[a]anthracene are described. Treatment of trans-5-azido-5,6-dihydrobenzo[c]phenanthren-6-ol ( 3 ) and trans-6-azido-5,6-dihydrobenzo[c]phenanthren-5-ol ( 5 ) with thionyl chloride yielded the corresponding β-chloro azides, which in turn, were reacted with lithium aluminium hydride to give 4b,5a-dihydro-5H-benzo[3,4]-phenanthro[1,2-b]azirine ( 2 ). In a similar manner trans-5-azido-5,6-dihydro-7,12-dimethylbenz[a]anthracen-6-ol ( 11 ) and trans-6-azido-5,6-dihydro-7,12-dimethylbenz[a]anthracen-5-ol ( 13 ) were transformed to the respective chloro azides and, converted into 1a,11b-dihydro-6,11-dimethyl-1H-benz[3,4]anthra[1,2-b]azirine ( 10 ).     

Complexes of Cu(II) and Pd(II) with 2-R-1,3,11,11<Emphasis Type="Italic">c</Emphasis>-tetraazacyclopenta[<Emphasis Type="Italic">c</Emphasis>]phenanthrenes

Paramagnetic complexes CuL¹SO₄·0.5H₂O, CuL²SO₄·2H₂O and diamagnetic Pd(HL²)Cl₃ (L¹ = 2-methyl-1,3,11,11c-tetraazacyclopenta[c]phenanthrene complex (L² = 2-phenyl-1,3,11,11c-tetraazacyclopenta-[c]phenanthrene) were synthesized. The most probable structure of the complexes was suggested on the basis of the IR and ESR spectra. Coordination units of paramagnetic complexes contain N atoms of the bidentate cycle-forming ligands, L¹ and L² molecules. The square PdCl₃N unit of the diamagnetic complex includes the N atom of the triazole fragment of the monodentate ligand, (HL²)⁺ cation.     

A New Class of Remote N‐Heterocyclic Carbenes with Exceptionally Strong σ‐Donor Properties: Introducing Benzo[c]quinolin‐6‐ylidene

We make the case for benzo[c]quinolin‐6‐ylidene ( 1 ) as a strongly electron‐donating carbene ligand. The facile synthesis of 6‐trifluoromethanesulfonylbenzo[c]quinolizinium trifluoromethanesulfonate ( 2 ) gives straightforward access to a useful precursor for oxidative addition to low‐valent metals, to yield the desired carbene complexes. This concept has been achieved in the case of [Mn(benzo[c]quinolin‐6‐ylidene)(CO)₅]⁺ ( 15 ) and [Pd(benzo[c]quinolin‐6‐ylidene)(PPh₃)₂(L)]²⁺ L=THF ( 21 ), OTf ( 22 ) or pyridine ( 23 ). Attempts to coordinate to nickel result in coupling products from two carbene precursor fragments. The CO IR‐stretching‐frequency data for the manganese compound suggests benzo[c]quinolin‐6‐ylidene is at least as strong a donor as any heteroatom‐stabilised carbene ligand reported.     

Transition metal complexes with bidentate ligands spanning trans-positions. IV. Preparation and properties of some rhodium and iridium complexes of 2,11-bis(diphenylphosphinomethyl)benzo [c]phenanthrene

The bidentate phosphine 2,11-bis(diphenylphosphinomethyl)benzo [c]phenanthrene ( 1 ) has been used to prepare the mononuclear, square planar complexes trans-[MX(CO)( 1 )] and trans-[M(CO)(CH₃CN)( 1 )][BF₄] (M = Rh, Ir; X = Cl, Br, I, NCS). It is found that the tendency of these complexes to form adducts with CO, O₂ and SO₂ is significantly lower than that of the corresponding Ph₃P complexes. The oxidative-addition reactions of complexes trans-[IrX (CO) ( 1 )] with hydrogen halides give the six-coordinate species [IrHX₂(CO) ( 1 )]. The complexes [IrH₂I (CO) ( 1 )] and [IrH₂L (CO) ( 1 )] [BF₄] (L = CO and CH₃CN) have been obtained from hydrogen and the corresponding substrates. The model compounds trans-[MCl (CO) (Ph₂PCH₂Ph)₂] (M = Rh, Ir), trans-[Ir (CO) (CH₃CN) (Ph₂PCH₂Ph)₂] [BF₄], [IrHCl₂(CO)(Ph₂PCH₂Ph)₂] and [IrH₂(CO)₂(Ph₂PCH₂Ph)₂] [BF₄] have been prepared and their special parameters are compared with those of the corresponding complexes of ligand 1 . The influence of the static requirements of this ligand on the chemistry of its rhodium and iridium complexes is discussed.     

The synthesis of novel polycyclic heterocyclic ring system via photocyclization. 18. Benzo[h]naphtho-[1′,2′:4,5]thieno[2,3-c]quinoline and benzo[h]naphtho-[1′,2′:4,5]thieno[2,3-c] [1,2,4]triazolo[4,3-a]quinoline

The synthesis of two previously unknown polycyclic ring systems, benzo[h]naphtho[1′2′:4,5]-thieno[2,3-c]quinoline ( 1 ) and benzo[h]naphtho[1′,2′:4,5]thieno[2,3-c][1,2,4]triazolo[4,3-a]quinoline ( 2 ), was achieved via oxidative photocyclization of 1-chloro-N-(1-naphthyl)naphtho[2,1-b]thiophene-2-carboxamide ( 5 ). The total assignment of their ¹H and ¹³C nmr spectra was determined by the concerted use of two-dimensional nmr methods.     

Transition metal complexes with bidentate ligands spanning trans-positions. Part XIV. Some complexes of 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene with platinum (0) and their reactivities

The ligand 2,11-bis(diphenylphosphinomethyl)benzo[c]phenanthrene ( 1 ) has been used to prepare complexes of the type [PtL( 1 )] (L ? C₂H₄, CH₂?CH? CO₂Me, PhC?CPh, MeC?CMe, MeO₂CC?CCO₂Me, (i-Pr)O₂CC?CCO₂(i-Pr), Ph₃P and CO). It is shown that these complexes are less labile than the corresponding species [PtL(Ph₃P)₂]. The preparation of complexes trans-[PtX(R)(1)] by oxidative addition of RX (RX ? PhCH₂Br and Mel) to [Pt(C₂H₄)(1)] is described. The isolation of [PtO₂(CH₃)₂CO(1)] is also reported.