Metallaborane reaction chemistry. A predicted and found tailored facile and reversible capture of SO2 by a B-frame-supported bimetallic: structures of [(PMe2Ph)2PtPd(phen)B10H10] and [(PMe2Ph)2Pt(SO2)Pd(phen)B10H10

The formally closo twelve-vertex {ortho-M2B10} dimetallaborane system has been predictively tailored for reversible uptake of SO2 across the metal-metal bond, as exemplified by the formation of [(PMe2Ph)2Pt(SO2)Pd(phen)B10H10] from [(PMe2Ph)2PtPd(phen)B10H10].     

The capture of dioxygen, carbon monoxide and sulfur dioxide by [(PMe2Ph)4Pt2B10H10

The metal-metal bond in [(PMe2Ph)4Pt2B10H10], from reaction of [PtCl2(PMe2Ph)2] or PMe2Ph with [(PMe2Ph)2PtB10H12], very readily, and readily reversibly, takes up atmospheric O2 to give the peroxidic dioxygen-dimetallaborane complex [(PMe2Ph)4(O2)Pt2B10H10], which has Pt-Pt 2.7143(3), Pt-O 2.141(4) and 2.151(4), and O-O 1.434(6)A. The {Pt2O2} bonding mode is fluxional. Compound irreversibly takes up CO to give the bridging-carbonyl-dimetallaborane complex [(PMe2Ph)4(CO)Pt2B10H10] which has a CO vector radial to the cluster, with Pt-Pt 2.7488(3), Pt-C 2.104(6) and 2.113(6), and C-O 1.163(6)A; CO readily displaces O2 from to give 3. SO2 similarly reacts with either or to give [(PMe2Ph)4(SO2)Pt2B10H10], which has tetrahedral sulfur, with Pt-Pt 2.8194(4), Pt-S 2.350(2) and 2.381(3), and S-O 1.470(8)A and 1.477(9)A.     

Macropolyhedral boron-containing cluster chemistry. Synchrotron X-ray structural analysis of [(PMe2Ph)2Pd2B16H20(PMe2Ph)2] and [(PMe2Ph)3Pt2B16H18(PMe2Ph)]: models of intermediates to more condensed metallaboranes from the [(PMe2Ph)2PtB8H12] thermolysis system

Thermolyses of [(PMe2Ph)2PdB8H12] and [(PMe2Ph)2PtB8H12] respectively yield eighteen-vertex [(PMe2Ph)2Pd2B16H20(PMe2Ph)2] and [(PMe2Ph)3Pt2B16H18(PMe2Ph)], which exhibit structure models for probable successive precursive intermediates for the more condensed macropolyhedral metallaboranes [(PMe2Ph)4Pt3B14H16], [(PMe2Ph)2Pt2B12H16] and [(PMe2Ph)2Pt2B16H15(C6H4Me)(PMe2Ph)] that have previously been reported as products from [(PMe2Ph)2PdB8H12] thermolyses.     

Macropolyhedral boron-containing cluster chemistry. The reaction of B16H20 and B14H18 with [PtMe2(PMe2Ph)2] to give [(PMe2Ph)2PtB16H17Me] and [(PMe2Ph)2PtB14H16

Structurally characterised 17-vertex [(PMe2Ph)2PtB16H17Me] 3 is obtained, albeit in low yield, by platination of 16-vertex B16H20 1 using [PtMe2(PMe2Ph)2] under mild conditions. Platination has occurred on the {B10} subcluster of 1, interesting in that B16H20 itself deprotonates on the {B8} subcluster: the reference 16-vertex [B16H19]- anion 1a, prepared by deprotonation of 1 with 1,8-bis(dimethylamino)naphthalene, is also structurally characterised. [PtMe2(PMe2Ph)2] with 14-vertex B14H18 2 similarly gives a low yield of 15-vertex [(PMe2Ph)2PtB14H16] 5, of formulation and structure substantiated by DFT calculations.     

Macropolyhedral boron-containing cluster chemistry. Novel intercluster linkages from the reaction of [Pt(cod)Cl2] and [PtMe2(PMe2Ph)2] with 6,6'-(B10H13)2O

6,6'-(B10H13)2O with [Pt(cod)Cl2] gives the [(B10H13OB10H11)Pt-{(B10H10OB10H12)]2- anion in which, uniquely, the units are held together by a B-O-B linkage in combination with a B-B linkage; with [PtMe2(PMe2Ph)2] it gives [(PMe2Ph)2PtB10H10-O,H-B10H11Pt(PMe2Ph)] in which, uniquely, the units are held together by an unsupported hydrogen-to-metal linkage as well as a B-O-B linkage.     

The reaction between [Pt(cod)Cl(PMe2Ph)]BF4 and aryltrimethyltin compounds

The complex [Pt(cod)Cl(PMe₂Ph)]BF₄ reacts in dichloromethane with SnArMe₃ compounds having Ar = 2-thienyl, 2-benzol [b]thienyl, or 2-benzo[b]furyl to give air-stable cationic aryl complexes [Pt(cod)Ar(PMe₂Ph)]BF₄. No reaction takes place when Ar  Ph. The cod ligand in the new complexes can be readily replaced by ligands such as PMe₂Ph, dppe, or 4-dimethylaminopyridine. The¹H and³¹P-{¹H} NMR parameters of the various complexes are reported.     

Sterically-induced low temperatur polyhedral rearrangements of carbaplatinaboranes: Synthesis and crystal structures of 1-Ph-3,3-(PMe2Ph)2-3,1,2-PtC2B9H10, 1-Ph-3,3-(PMe2Ph)2-3,1,11-PtC2B9H10, 11-Ph-3,3-(PMe2Ph)2-3,1,11-PtC2B9H10 and 1,11-Ph2-3,3-(PMe2Ph)2-3,1,11-PtC2B9H9

Reaction of cis-Pt(PMe₂Ph)₂Cl₂ with Tl₂[7-Ph-7,8-nido-C₂B₉H₁₀] affords 1-Ph-3,3-(PMe₂Ph)₂-3,1,2-PtC₂B₉H₁₀, mild thermolysis (55°C) of which yields 1-Ph-3,3-(PMe₂Ph)₂-3,1,11-PtC₂B₉H₁₀ and 11-Ph-3,3-(PMe₂Ph)₂-3,1,11-PtC₂B₉H₁₀. Both of the latter compounds are produced by the microwave irradiation of a mixture of cis-Pt(PMe₂Ph)₂Cl₂ and [HNMe₃][7-Ph-7,8-nido-C₂B₉H₁₁]. When cis-Pt(PMe₂Ph)₂Cl₂ is allowed to react with Tl₂[7,8-Ph₂-7,8-nido-C₂B₉H₉] at room temperature the only isolable species is 1,11-Ph₂-3,3-(PMe₂Ph)₂-3,1,11-PtC₂B₉H₉. The generation of rearranged products with 3,1,11-PtC₂B₉ architectures is inconsistent with a diamond-square-diamond mechanism for the isomerisation of icosahedral heteroboranes.     

The preparation and molecular structure oftrans-[MoCl2(PMe2Ph)4]

Summary The compoundtrans-[MoCl₂(PMe₂Ph)₄] has been prepared by the reduction of MoCl₅ (by Mg) or of [MoCl₃(PMe₂Ph)₃] (by LiBuⁿ) in the presence of PMe₂Ph in tetrahydrofuran (THF). It has _eff=2.84 B.M. and crystallises in space group P1 witha=11.591(3),b=12.931(3),c=12.703(3) Å, = 95.28(2), =105.97(2), =103.54(2)°. Refinement of the structure gave R=0.036. The Mo-Cl and Mo-P distances average 2.443(6) and 2.534(8) Å, respectively.Low-valent phosphine complexes of the Group VI metals continue to attract much attention because of their involvement in studies of the catalytic activation of dinitrogen⁽¹⁾, dihydrogen(^{2, 3}), alkenes and alkynes(⁴). As a by-product during our studies of dinitrogen(¹) and hydride(²) complexes of molybdenum and tungsten, we obtainedtrans-[MoCl_2- (PMe₂Ph)₄] as yellow, paramagnetic crystals (_eff= 2.84 B.M.). We first obtained the compound during the attempted synthesis ofcis-[Mo(N₂)₂(PMe₂Ph)₄] by reduction of MoCl₅ with Mg in the presence of PMe₂Ph (see Experimental). Upon identification of the compound we found that it could be readily synthesised by treatment of [MoCl₃(PMe₂Ph)₃]⁽⁵⁾ with LiBuⁿ in THF in the presence of PMe₂Ph (experimental).The complex was shown to have thetrans structure by x-ray analysis (Figure). Analogues oftrans-[MoCl₂(PMe₂Ph)₄] have been prepared, namely [CrCl₂(Me₂PCH₂CH₂PMe₂)₂]⁽⁶⁾,trans- [MoCl₂(PMe₃)₄]⁽⁷⁾, [WCl₂(PMe₂Ph)₄]⁽⁸⁾ and [WCl₂(PMe₃)₄]⁽⁴⁾, of which onlytrans-[MoCl₂(PMe₃)₄] has been examined by X-rays⁽⁷⁾. Its principal structural parametersi.e. d(Mo-Cl)= 2.420(6), d(Mo-P)_av=2.496(3) Å⁽⁶⁾ are close to those found here fortrans-[MoCl₂(PMe₂Ph)₄].     

Synthesis of elliptical vanadoborates housing bimetallic centers [Zn4(B2O4H2)(V10B28O74H8)]8- and [Mn4(C2O4)(V10B28O74H8)]10-

The hydrothermal synthesis of three new vanadoborate compounds with elliptical (V10B28O74H8) clusters is described. The clusters contain pairs of bimetallic Zn2 or Mn2 units.     

The reaction of diphenyltin (IV) or triphenyltin (IV) chloride with 3,4,5-trimethoxybenzoyl salicylahydrazone. The crystal structure of Ph2[(MeO)3C6H2C(O)N2CHC6H4O]Sn

The title complex has been synthesized by the reaction of diphenyltin(IV) or triphenyltin(IV) chloride with 3,4,5-trimethoxybenzoyl salicylahydrazone and characterized by ¹H, ¹³C, ¹¹⁹Sn NMR, and IR spectral studies. An X-ray analysis shows that the ligand is tridentate and approximately planar and the central tin atom is in a distorted five-coordinate trigonal bipyramidal geometry. The complex crystallizes in the monoclinic space group C2/c with a = 29.194(4), b = 10.117(1), c = 22.524(3) Å, β = 124.44(2)°, V = 5486.5(8) ų, Z = 8. The Sn C bond lengths are 2.123(9) and 2.116(7) Å, and the bond length between the tin atom and the coordinating nitrogen atom (Sn–N bond) is 2.152(6) Å. The C Sn C bond angle and the bond angle between the tin atom and the two axially positioned oxygen atoms are 129.1(1) and 156.17(9)°, respectively. The structure was refined to final R = 0.056 and R_w = 0.074 for 4145 observed reflections with I > 3σ(I). © John Wiley & Sons, Inc.     

Crystal structure and optical spectroscopy of Er2[Pt(CN)4]3.21H2O and Er2[Pt(CN)4]2.SO4.11.5H2O

We have synthesized two forms of erbium tetracyanoplatinates, Er2[Pt(CN)4]3.21H2O (red form) and Er2[Pt(CN)4]2.SO4.11.5H2O (yellow form), and determined their crystal structures by X-ray diffraction. While the red form crystallizes in the orthorhombic space group Pbcn, with a = 15.4848(3) A, b = 13.8186(2) A, c = 19.07820(10) A, alpha = beta = gamma = 90 degrees, and Z = 4, the yellow form precipitates in the tetragonal space group I4cm, with a = b = 14.321(2) A, c = 13.338(3) A, alpha = beta = gamma = 90 degrees, and Z = 4. Both forms show [Pt(CN)4]2- chains but differ markedly in color and morphology. This is due to the incorporation of sulfate ions in the latter modification, leading to an increased Pt-Pt distance. The observed optical absorption and emission behavior of the title compounds is correlated with the Pt-Pt distances.     

(Zr6B)Cl12(MeCN)6][Ph4B].1.6MeCN: an easily-accessible starting material for zirconium cluster chemistry and [(Zr6B)Cl12(Pyr6)][Ph4B].2{(PyrH)[Ph4B]}, a first reaction product

In an attempt to produce a convenient starting material for the development of new interstitially centered, octahedral zirconium cluster compounds by solution-chemical methods, a new approach, using Na[Ph4B] to withdraw all six outer chlorides by precipitating them as NaCl, was explored. From a solution of K 2[(Zr 6B)Cl15] and Na[Ph4B] in acetonitrile, the tetraphenylborate salt [(Zr6B)Cl12(MeCN)6][Ph4B].1.6 MeCN (1) was obtained with high yield. It contains the [(Zr6B)Cl(i)12(MeCN)(a)6](+) ion (2) with an octahedral metal core. The crystal structure of 1, which possesses high solubility in several organic solvents, is reported. Treatment of 1 with pyridine gave the new cluster phase [(Zr6B)Cl12(Pyr6][Ph4B].2{(PyrH)[Ph4B]} (3), which was characterized as well by X-ray crystallography. An advantage of both title phases is that they contain Lewis acidic zirconium cluster units, which might be useful as catalysts, with the additional advantage of tuneable redox properties.     

The first bismuth phosphonate cluster. X-ray single crystal structure of [(ButPO3)10(ButPO3H)2Bi14O(10).3C6H(6).4H2O

The reaction of triphenylbismuth and tert-butylphosphonic acid gives the bismuth phosphonate phase (ButPO3H)3Bi and the first bismuth phosphonate cluster [(ButPO3)10(ButPO3H)2Bi14O(10).3C6H(6).4H2O].     

Cluster chemistry XXIV. X-ray structure of H4 Ru4(CO)9(PMe2 Ph)[P(OC6H4 Me-p)3]-[P(OCH2)3CEt], a chiral cluster complex containing four different ligands

The X-ray structure of H₄Ru₄(CO)₉(PMe₂Ph)[P(OC₆H₄Me-p)₃][P(OCH₂)₃CEt], a chiral cluster complex, has been determined. The complex is triclinic, space group P$\text{1}$, a 19.812(7), b 14.299(4), c 10.323(4) Å, α 100.09(3), β 98.18(3), γ 102.23(3)°. The unit cell contains an enantiomeric pair of molecules. The Ru₄ core contains two short (av. 2.785 Å) and four long (2.967 Å) RuRu separations with approximate D_2d symmetry. RuP separations are 2.254(6) Å [to P(OCH₂)₃CEt], 2.270(6) Å [to P(OC₆H₄Me-p)₃] and 2.326(7) Å [to PMe₂Ph]; all P-donor ligands are trans to short RuRu vectors.     

A Triple Cluster Platinaborane：[（P（2）Ph3）Pt（1）（μ2—B（11）—B（9）—OC（CH3）3—B10H10））Pt（7）（P（1）Ph3）]2

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