Treatment of 1,8-bis(diphenylphosphino)naphthalene (dppn, 1) with stoichiometric amounts of sulfur or selenium in toluene at 80°C selectively afforded the diphosphine monochalcogenides 1-Ph 2 P(C 10 H 6 )-8-P(:S)Ph 2 (dppnS, 2 a) and 1-Ph 2 P(C 10 H 6 )-8-P(:Se)Ph 2 (dppnSe, 2 b). The 31 P{ 1 H} NMR spectrum of 2 b showed an unusually large 5 J(P±Se) value, which indicates a significant through-space coupling component. The monosulfide acted as a bidentate P,S-ligand towards platinum(II) (3 a), whereas the corresponding monoselenide complex (3 b') lost elemental selenium with formation of the previously reported complex [PtCl 2 (dppn)-P,P'] (3). Treatment of dppnSe with [(nor)Mo(CO) 4 ] (nor = norbornadiene) led to formation of [(dppnSe)Mo(CO) 4 -P,Se] (3 b). Solutions of the latter slowly deposited Se with formation of [(dppn)Mo(CO) 4 -P,P'] (4) which was also obtained by independent synthesis from 1 and [(nor)Mo(CO) 4 ].All isolated new compounds were characterised by a combination of 31 P, 1 H, 13 C and 77 Se (2 b) NMR spectroscopy, IR spectroscopy, mass spectrometry and elemental analysis. Single-crystal X-ray structure determinations were performed for dppnSe (2 b), [PtCl 2 (dppnS)-P,S] (3 a), [(dppnSe)Mo-(CO) 4 -P,Se] (3 b) and [(dppn)Mo(CO) 4 -P,P'] (4). In 2 b steric effects cause the naphthalene ring to be distorted and force the phosphorus atoms by 65 and 59 pm to opposite sides of the best naphthalene plane. In the metal complexes 3 a, 3 b and 4 the phosphino-phosphinochalcogenyl systems act as bidentate ligands through the P and the chalcogen atoms. The naphthalene systems are again distorted. The two independent molecules of 4 differ in their conformations.Einfach oxidierte Schwefel-und Selen-Derivate von 1,8-Bis(diphenylphosphino)naphthalin: Synthese und Koordinationschemie Inhaltsu È bersicht. Die Umsetzung von 1,8-Bis(diphenylphosphino)naphthalin (dppn, 1) mit sto È chiometrischen Mengen Selen oder Schwefel in Toluol bei 80°C fu È hrte selektiv zu den Diphosphin-Monochalkogeniden 1-Ph 2 P(C 10 H 6 )-8-P(:S)Ph 2 (dppnS, 2 a) und 1-Ph 2 P(C 10 H 6 )-8-P(:Se)Ph 2 (dppnSe, 2 b). Das 31 P{ 1 H} NMR Spektrum von 2 b zeigte einen ungewo È hnlich groûen Wert fu È r 5 J(P±Se), der auf eine signifikante Wechselwirkung durch den Raum deutet (through-space coupling). Das Monosulfid fungierte als zweiza È hniger P,S-Ligand gegenu È ber Platin(II) (3 a), wa È hrend sich der entsprechende Komplex des Monoselenids (3 b') unter Abscheidung elementaren Selens schnell in den bekannten Komplex [PtCl 2 (dppn)-P,P'] (3) umwandelte. Die Umsetzung von dppnSe mit [(nor)Mo(CO) 4 ] (nor = Norbornadien) fu È hrte zur Bildung von [(dppnSe)Mo(CO) 4 -P,Se] (3 b). Aus Lo È sungen dieses Komplexes in Dichlormethan schied sich langsam elementares Selen ab, wobei sich [(dppn)Mo(CO) 4 -P,P'] (4) bildete. Letzterer Komplex konnte auch durch unabha È ngige Synthese aus dppn und [(nor)Mo(CO) 4 ] hergestellt werden. Alle isolierten neuen Verbindungen wurden durch eine Kombination von 31 P, 1 H, 13 C und 77 Se (2 b) NMR-Spektroskopie, IR...
The synthesis and characterisation of the reactive tetrakis(0,O-phosphorus)-bridged calix[4]resorcinols 3 and 4 is described. Because of its poor solubility in common organic solvents, a solid-state NMR investigation of 3 (lH, 13C, 'lP) was conducted. Reaction of 3 with MeMgI, Me,SiNMe2, and HNMe2 furnished the 03h3P-substituted cavitands 5 and 6. Oxidative addition reactions of 6 with the (H2N)2C(=O)/H202(1: 1) adduct, tetrachloro-o-benzoquinone (TOB), and hexafluoroacetone (HFA) led to the n4h5P derivative 7, and to the n5h5P derivatives 8 and 9. An X-ray crystal-structure determination of the tetrakis(0,O-phosphorus)-bridged calix[4]resorcinol 4 has been conducted. The framework displays the cone conformation; the chlorine atoms are directed inwards.
The acid‐catalyzed (with HCl) condensation reactions of resorcinol (1) with 1‐naphthaldehyde (2) and isobutyraldehyde (3) furnished the tetrameric macrocyclic compounds 4 and 6. Detailed NMR‐investigations of the acetylated tetrameric species 5 surprisingly support a structure not in agreement with the expected all‐cis conformation. The chair conformation (C2h symmetry) of the acetylated derivative 5 was established through a crystal X‐ray diffraction study. The naphthyl substituents are arranged in trans position above and below the plane made up by the resorcinol units. The reaction of resorcinol 1 with isobutyraldehyde, in accord with expectation, led to the calix[4]resorcinaren (6). The 1H NMR spectra of compound 6 and 7 appeared at room temperature as broad signals, indicating a conformation of C2v symmetry. The reaction of the C‐methyl‐tetrakis‐P‐(chlorodioxaphosphocin)‐calix[4]resorcinarenes (8) and (10) with suitable N‐trimethylsilyl organic amines were conducted in tetrahydrofuran suspension, furnishing the P–N‐substituted calix[4]resorcinarenes (9) and (11). While in the complexation of C‐methyl‐tetrabromotetrakis‐P‐(dimethylaminodioxaphosphocin)‐calix[4]resorcinarene (13) with (tht)AuCl (tht = tetrahydrothiophene) the expected, neutral tetra‐substituted complex 15 was formed, the reaction of 13 with moist acetonitrile led to the anionic atomic framework 14. X‐ray structure determinations of the complexes 14 and 15 show that both possess the cone conformation. In the gold complex 15, the Au–Cl groups form a loose aggregate, with three Au…Cl contacts of 316–340 pm; one of the groups points towards the centre of the cone. The copper(I) complex 14 displays crystallographic mirror symmetry, with a central Cu4Cl5 unit involving tetrahedrally coordinated copper.
A representative series of diphosphine monophosphonium salts [1-Ph 2 P(C 10 H 6 )-8-PRPh 2 ] + X ± (2 b: R = H, X = CF 3 SO 3 ; 4: R = Me, X = CF 3 SO 3 ; 5: R = C 6 H 5 CH 2 = Bn, X = Br) has been prepared by treatment of 1,8-bis(diphenylphosphino)naphthalene (dppn, 1) with stoichiometric amounts of HSO 3 CF 3 or CH 3 SO 3 CF 3 in CH 2 Cl 2 at +20°C and with C 6 H 5 CH 2 Br in toluene at +80°C. Their X-ray crystal structures show that there is no evidence for dative P ® P + interactions. Instead, steric repulsion deflects the substituent groups to opposite faces of the naphthalene plane [splay angles: +11.4°(2 b), +13.6°(4); +16.7°(5)]. In solution 2 b, 4, and 5 were dynamic according to 31 P, 13 C, and 1 H NMR spectroscopy. The fluxionality of 2 b involves rapid intramolecular proton exchange between the two phosphorus atoms, which slows down at low temperature, whereas the dynamic behaviour of 4 and 5 is interpreted in terms of hindered rotation of the bulky RPh 2 P + groups (R = Me or Bn) about the P±C(naphthyl) bond. Treatment of 1,8-bis(diphenylphosphoryl)naphthalene (dppnO 2 , 6) with HSO 3 CF 3 gave the protonated bis(phosphine oxide), as the triflate salt, dppnO 2 H + CF 3 SO 3 ± (7). The X-ray structure analysis of 7 revealed a highly strained molecule (P1´´´P2 365.5 pm) in which the P=O bonds point to the same face of the naphthalene plane to accommodate the proton. All isolated compounds were characterised by a combination of 31 P, 1 H, and 13 C NMR spectroscopy, IR spectroscopy (7), mass spectrometry and elemental analysis.Phosphonium-Salze von 1,8-Bis(diphenylphosphino)naphthalin: Moleku È lstrukturen und NMR-spektroskopische Untersuchungen Inhaltsu È bersicht. Durch Umsetzung von 1,8-Bis(diphenylphosphino)naphthalin (dppn, 1) mit sto È chiometrischen Mengen HSO 3 CF 3 oder CH 3 SO 3 CF 3 in CH 2 Cl 2 bei +20°C und mit C 6 H 5 CH 2 Br in Toluol bei +80°C wurde eine repra È-sentative Reihe von Diphosphin-Monophosphoniumsalzen [1-Ph 2 P(C 10 H 6 )-8-PRPh 2 ] + X ± (2 b: R = H, X = CF 3 SO 3 ; 4: R = Me, X = CF 3 SO 3 ; 5: R = C 6 H 5 CH 2 = Bn, X = Br) hergestellt. Die Ro È ntgenstrukturanalysen ergeben keine Hinweise auf dative, bindende P ® P + Wechselwirkungen. Stattdessen fu È hrt sterische Abstoûung zu einer Ablenkung der Substituenten auf entgegengesetzte Seiten der NaphthalinEbene [Spreizwinkel: +11.4°(2 b), +13.6°(4); +16.7°(5)]. In Lo È sung zeigten 2 b, 4 und 5 bei 31 P-, 13 C-und 1 H-NMRspektroskopischen Untersuchungen dynamisches Verhalten. Bei 2 b handelt es sich um einen schnellen, intramolekularen Protonenaustausch zwischen den beiden Phosphoratomen, der bei niedrigen Temperaturen verlangsamt ist, wa È hrend das dynamische Verhalten von 4 und 5 durch gehinderte Rotation der sperrigen RPh 2 P + Gruppen (R = Me oder Bn) um die P±C(Naphthyl) Bindung erkla È rt werden kann. Die Umsetzung von 1,8-Bis(diphenylphosphoryl)naphthalin (dppnO 2 , 6) mit HSO 3 CF 3 fu È hrte zum protonierten Bis(phosphinoxid), in Form des Triflatsalzes, dppnO 2 H + CF 3 SO 3 ± (7). Die Ro È ntgenstrukturanalyse von...
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