Synthesis and structural behavior of the P-functional organotin chlorides [Ph2P(CH2)3]2SnCl2, Ph2P(CH2)3SnCl2Me, and Ph2P(CH2)nSnCl3 (n=2, 3)

The P-functional organotin dichloride [Ph₂P(CH₂)₃]₂SnCl₂ (3) is synthesized by reaction of Ph₂P(CH₂)₃MgCl with SnCl₄ independently of the molar ratio of the starting compounds. The corresponding organotin trichlorides Ph₂P(CH₂)_nSnCl₂R (4: n=2, R=Cl; 5: n=3, R=Cl; 6: n=3, R=Me) are formed in a cleavage reaction of Ph₂P(CH₂)_nSnCy₃ (n=2, 3) with SnCl₄ or MeSnCl₃, respectively. The main features of the crystal structures of 3–6 are both intra- and intermolecular PSn coordinations and the existence of intermolecular Sn---ClSn bridges. For further characterization of the title compounds, the adducts 4(Ph₃PO)₂ (7) and 5(Ph₃PO) (8), as well as the P-oxides and P-sulfides of 3–6 (9–15), are synthesized. The results of crystal structure analyses of 7, 11, 12, and 14 are reported. The structures of 9–15 are characterized by intramolecular P=XSn interactions (X=O, S). A first insight into the structural behavior of the compounds 3–15 in solution is discussed on the basis of multinuclear NMR data.     

Synthese und Kristallstruktur von Ammin(μ3‐L‐glutamato)kupfer(II)

Synthesis and Crystal Structure of Ammine(μ₃‐L‐glutamato)copper(II) [Cu(L‐Glu)H₂O]·H₂O reacts with aqueous ammonia to give the ammine complex [Cu(L‐Glu)NH₃] ( 1 ). 1 forms orthorhombic crystals, space group P 2₁2₁2 with a = 1585,1(1) pm; b = 979,46(7) pm and c = 504,70(5) pm. In the crystal structure of 1 the copper atoms are linked by μ₃‐glutamate units to give a 2D layer structure. The copper atoms exhibit a square‐pyramidal coordination with two N atoms and two O atoms in the base plane and one O atom at the apex of the pyramid. The crystal structure is stabilized by a 3D network of N–H···O hydrogen bridges.     

Thallium(I), Silver(I), and Mixed Thallium(I)/Copper(I) Clusters with Bridging {Me2Si(N‐C6H4‐2‐SPh)2}2– Ligands

The S‐functionalized aminosilane Me₂Si(NH‐C₆H₄‐2‐SPh)₂ (H₂L) ( 1 ) was prepared from dichlorodimethylsilane and lithiated 2‐(phenylthio)aniline. Treatment of compound 1 with two equivalents of n‐butyllithium led to the dilithium derivative Li₂L, which was used in subsequent reactions with MCl (M = Tl, Cu, Ag) to prepare the complexes [Tl₂L] ( 2 ), [Cu₂Tl₂L₂] · 2THF ( 3a ), [Cu₂Tl₂L₂(THF)₂] ( 3b ), and [Ag₄L₂(THT)₂] ( 4 ) (THT = tetrahydrothiophene). Compound 2 consists of two thallium atoms, which are connected by a L^2– ligand to give a puckered Tl₂N₂ ring with Tl–N distances of 255(1)–268(1) pm. Compounds 3a and 3b are heterobimetallic complexes, which are based on [Cu₂L₂]^2– cores featuring a Cu₂N₄Si₂ ring with linearly coordinated copper atoms [Cu–N: 190.7(3)–192.5(3) pm] and two peripherally attached Tl atoms [Tl–N: 272.7(3)–281.9(3) pm]. The molecular structure of the tetranuclear silver(I) complex 4 is closely related to the structure of compounds 3a and 3b by replacement of the Cu and Tl atoms with Ag atoms. The Ag–N distances are 217.5(3)–245.7(3) pm.     

Concise Synthesis of Both Enantiomers of Pilocarpine

Furan-2-carboxylic acid was used as a starting material for the synthesis of dehydro-homopilopic acid. Esterification, hydrogenation and enzymatic hydrolysis followed by the reduction of Weinreb amides and a single-step attachment of a 1-methyl-imidazole residue allowed for the concise synthesis of both enantiomers of pilocarpine.     

Neue [{Cp(CO)2Mo}2ESbCl]‐Cluster mit tetraedrischem Mo2SbE‐Gerüst (E = S,Se)

Reaction of [{Cp(CO)₃Mo}₂SbCl] with S₈ or Se₈ leads to the formation of cluster compounds [{Cp(CO)₂Mo}₂ESbCl] (E = S, Se). [{Cp(CO)₂Mo}₂SSbCl] crystallizes monoclinic, space group P2₁/n with a = 812.28(3), b = 855.65(4), c = 2441.01(9) pm and β = 90.149(3)°; [{Cp(CO)₂Mo}₂SeSbCl] · CH₂Cl₂ crystallizes triclinic, space group P$\bar{1}$ with a = 828.82(9), b = 1002.8(1), c = 1340.0(2) and α = 109.24(1), β = 100.87(1), γ = 96.81(1)°. For both compounds X‐ray crystal structure analysis reveals tetrahedral Mo₂SbE cluster cores with Sb–E bond lengths of 256.8(1) pm (E = S) and 265.3(1) (E = Se). According to the 18 electron rule the [{Cp(CO)₂Mo}₂ESbCl] clusters can be regarded as complexes of the 4 electron donator ESbCl that is coordinated “side‐on” to a {Cp(CO)₂Mo}₂ fragment.     

Synthese und Eigenschaften von Ph3Sn‐substituierten Telluraten – Die Kristallstrukturen von trans‐[(Ph3SnO)4Te(OH)2] und trans‐[(Ph3SnO)2Te(OMe)4]

The reaction of Te(OH)₆ with Ph₃SnOH in ethanol leads to the formation of trans‐[(Ph₃SnO)₄Te(OH)₂] ( 1 ). Compound 1 crystallizes triclinic in the space group P\bar{1} with a = 996.6(2) pm, b = 1365.4(3) pm, c = 1368.2(3) pm and α = 71.15(2)°, β = 71.48(2)°, γ = 74.81(3)° (at 220 K). The molecular structure of 1 consists of a tellurium atom, which is coordinated nearly octahedrally by four Ph₃SnO units and two hydroxyl groups that are trans to each other. The Te–O bond lengths are in the range of 190.5(2) and 193.7(2) pm. Treatment of 1 with methanol under reflux yields trans‐[(Ph₃SnO)₂Te(OMe)₄] ( 2 ). Compound 2 crystallizes triclinic in the space group P\bar{1} with a = 1012.8(1) pm, b = 1422.4(2) pm, c = 1618.1(2) pm, and α = 100.44(1)°, β = 107.92(1)°, γ = 110.66(1)° (at 220 K). 2 forms centrosymmetric molecules in which the tellurium atom is surrounded nearly octahedrally by four methoxy groups and two trans arranged Ph₃SnO units. The Te–O bond lengths of 187.9(3)–194.5(3) pm are similar to those observed in 1 .     

Synthesis and Crystal Structures of Lithium,Sodium, and ­Potassium Derivatives of 2‐(Methylthio)aniline and 2‐(Phenylthio)aniline

2‐(Methylthio)aniline (H₂L¹) and 2‐(phenylthio)aniline (H₂L²) were treated with n‐butyllithium to yield the corresponding anilides [LiHL¹] and [LiHL²]. Recrystallization from diethyl ether and THF afforded the solvates [LiHL¹(Et₂O)] and [LiHL²(THF)₂]. The X‐ray crystal structure determination revealed dimeric molecules which exhibit a centrosymmetric Li₂N₂ ring. In the case of [LiHL¹(Et₂O)] the SMe group is involved in Li coordination and in the case of [LiHL²(THF)₂] the SPh group is part of an intramolecular N–H ··· S hydrogen bridge. The sodium anilides [NaHL¹(DME)] and [NaHL²(DME)] were obtained from the reaction of H₂L¹ and H₂L² with sodium amide in DME as solvent. Like in the case of the lithium amides the sodium derivatives [NaHL¹(DME)] and [NaHL²(DME)] display centrosymmetric Na₂N₂ cores. The coordination sphere of the sodium atoms is completed by DME molecules, which act as chelating ligands. In the case of [NaHL¹(DME)] the DME molecules enable additionally a linkage of the dimeric subunits to give a chain structure. The potassium derivatives [KNHL¹] and [KNHL²(DME)] were obtained from H₂L¹ and H₂L² and potassium hydride in DME as solvent. [KNHL¹] displays a distinct structure based on [(KNHL¹)₂] dimers, which are linked by additional [KNHL¹] units to give a 3D coordination polymer with {4.8.16(3)} topology. [KNHL²(DME)] forms dimers linked by bridging DME molecules to give a chain‐like coordination polymer.     

Koordinativ ungesättigte Dirutheniumkomplexe: Synthese und Kristallstrukturen von [Ru2(CO)4(μ‐H)(μ‐S)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] und [Ru2(CO)4(μ‐X)(μ‐PtBu2)(μ‐Ph2PCH2PPh2)] (X = Cl,S2CH)

Coordinatively Unsaturated Diruthenium Complexes: Synthesis and X‐Ray Crystal Structures of [Ru₂(CO)₄(μ‐H)(μ‐S)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)], [Ru₂(CO)₄(μ‐X)(μ‐P^tBu₂)(μ‐Ph₂PCH₂PPh₂)] (X = Cl, S₂CH) [Ru₂(CO)₄(μ‐H)(μ‐P^tBu₂)(μ‐dppm)] ( 1 ) reacts in benzene with elemental sulfur to the addition product [Ru₂(CO)₄(μ‐H)(μ‐S)(μ‐P^tBu₂)(μ‐dppm)] ( 2 ) (dppm = Ph₂PCH₂PPh₂). 2 is also obtained by reaction of 1 with ethylene sulfide. The reaction of 1 with carbon disulfide yields with insertion of the CS₂ into the Ru₂(μ‐H) bridge the dithioformato complex [Ru₂(CO)₄(μ‐S₂CH)(μ‐P^tBu₂)(μ‐dppm)] ( 3 ). Furthermore, 1 reacts with [NO][BF₄] to the complex salt [Ru₂(CO)₄(μ‐NO)(μ‐H)(μ‐P^tBu₂)(μ‐dppm)][BF₄] ( 4 ), and reaction of 1 with CCl₄ or CHCl₃ affords spontaneously [Ru₂(CO)₄(μ‐Cl)(μ‐P^tBu₂)(μ‐dppm)] ( 5 ) in nearly quantitative yield. The molecular structures of 2 , 3 and 5 were confirmed by crystal structure analyses.