Labile Ligands Research Articles

Rhenium(I) Tricarbonyl Complexes with (2-Hydroxyphenyl)diphenylphosphine as PO Bidentate Ligand.

In the present work, we investigated potential means to obtain neutral tricarbonyl mixed-ligand fac-[M(CO)3L1L2] complexes (M = Re, 99mTc) containing the (2-hydroxyphenyl)diphenylphosphine (POH) bidentate ligand (L1H) and a series of monodentate ligands (L2). First, fac-[Re(CO)3(PO)(H2O)], 1, was synthesized by reaction of POH and [Et4N]2[Re(CO)3Br3] in equimolar amounts in MeOH at room temperature. Interestingly, with excess of POH this reaction afforded fac-[Re(CO)3(PO)(POH)], 2, with POH operating both as a bidentate and as a monodentate ligand. Owing to the presence of the labile aqua ligand, which can be readily replaced by various monodentate ligands, 1 was further used as a precursor to generate a small library of the desired fac-[M(CO)3L1L2] complexes. Specifically, by reaction of triphenylphosphine (PPh3), imidazole (im), pyridine (py), cyclohexyl isocyanide (cisc), and tert-butyl isocyanide (tbi), the following products were readily obtained in excellent yields (92%-95%): fac-[Re(CO)3(PO)(PPh3)], 3, fac-[Re(CO)3(PO)(im)], 4, fac-[Re(CO)3(PO)(py)], 5, fac-[Re(CO)3(PO)(cisc)], 6, and fac-[Re(CO)3(PO)(tbi)], 7. All compounds were fully characterized by elemental analysis, IR and NMR spectroscopies, and electrospray ionization(+) mass spectrometry. Their solid-state structure was elucidated by X-ray crystallography. Of considerable interest is the fact that the corresponding 2'-7' were easily accessible at the 99mTc-tracer level in quantitative yields after reaction of POH and the respective monodentate ligand L2 with fac-[99mTc(CO)3(H2O)3]+ in aqueous MeOH, as verified by comparative chromatographic methods adopting dual photo- and radiometric detection modes. The high stability displayed by all 99mTc complexes during histidine and cysteine challenge assays underscored the suitability of the fac-[M(CO)3(PO)L2] system for radiopharmaceutical development purposes.

Design, Synthesis, and Chemistry of Bis(σ)borate and Agostic Complexes of Group 7 Metals.

A series of new bis(σ)borate and agostic complexes of group 7 metals have been synthesized and structurally characterized from various borate ligands, such as trihydrobis(benzothiazol-2-yl)amideborate (Na[(H3 B)bbza]), trihydro(2-aminobenzothiazolyl)borate (Na[(H3 B)abz]), and dihydrobis(2-mercaptopyridyl)borate (Na[(H2 B)mp2 ]) (bbza=bis(benzothiazol-2-yl)amine, abz=2-aminobenzothiazolyl, and mp=2-mercaptopyridyl). Photolysis of [Mn2 (CO)10 ] with Na[(H3 B)bbza] formed bis(σ)borate complex [Mn(CO)3 (μ-H)2 BHNCSC6 H4 (NR)] (1; R=NCSC6 H4 ). Octahedral complex [Re(CO)2 (N3 C2 S2 C12 H8 )2 ] (2) was generated under similar reaction conditions with [Re2 (CO)10 ]. Similarly, when [Mn2 (CO)10 ] was treated with Na[(H3 B)abz], bis(σ)borate complex [Mn(CO)3 (μ-H)2 BH(HN2 CSC6 H4 )] (3) and the agostic complex [Mn(CO)3 (μ-H)BH(HN2 CSC6 H4 )2 ] (4) were formed. To probe the potential formation of agostic complexes of the heavier group 7 metals, we carried out the photolysis of [M2 (CO)10 ] with Na[(H2 B)mp2 ] and found that [M(CO)3 (μ-H)BH(C5 H4 NS)2 ] (5: M=Re; 6: M=Mn) was formed in moderate yield. Complexes 1 and 3 feature a (κ3 -H,H,N) coordination mode, whereas 4, 5, and 6 display both (κ3 -H,N,N) and (κ3 -H,S,S) modes of the corresponding ligands. To investigate the lability of the CO ligands of 1 and 3, we treated the complexes with phosphine ligands that generated novel bis(σ)borate complexes [Mn(μ-H)2 (BHNCSC6 H4 )(NR)(CO)2 PL2 L'] (R=NCSC6 H4 ; 7 a: L=L'=Ph; 7 b: L=Ph, L'=Me) and [Mn(μ-H)2 BHN(NCSC6 H4 )R(CO)2 PL2 L'] (R=NCSC6 H4 ; 8 a: L=L'=Ph; 8 b: L=Ph, L'=Me). Complexes 7 and 8 are structural isomers with different coordination modes of the bbza ligand. In addition, DFT calculations were performed to shed some light on the bonding and electronic structures of these complexes.

One-pot synthesis of ferromagnetic FePd nanoparticles from single-source organometallic precursors and size effect of metal fraction in polymer chain

The accurate regulation of the size of the ferromagnetic nanoparticle synthesized from the one-pot pyrolysis of metallopolymer is a challenging topic to date. A bimetallic complex TPy-FePd-1 was prepared and used as a single-source precursor to synthesize ferromagnetic FePd nanoparticles (NPs) by one-pot pyrolysis. The resultant FePd NPs have a mean particle size of 19.8 nm and show a coercivity of 1.02 kOe. In addition, the labile ligand NCMe in TPy-FePd-1 was easily substituted by a pyridyl group. A random copolymer PS-P4VP was used to coordinate with TPy-FePd-1, and the as-synthesized metallopolymer made the metal fraction disperse evenly along the flexible chain. Investigation of FePd NPs from the bimetallic polymers with different metal fractions was also made, and the size of the resultant nanoparticles could be easily controlled by tuning the metal fraction in the polymer.

Theoretical determination of the aquation reaction mechanism of cyclometalated benzimidazole Ru(II) and Ir(III) anticancer complexes

The free energy profiles for the hydrolysis reaction mechanism of two synthesized C,N-cyclometalated benzimidazole chorido-Ir(III) and Ru(II) anticancer complexes, which have shown promising anticancer activity, have been explored theoretically employing density functional theory (DFT). Analogous calculations have been carried out for the complexes obtained by the substitution of either the H atom in R4 position of the phenyl ring of the 2-phenylbenzimidazole chelating ligand with the electron-withdrawing CF3 group or the chloride ligand with pyridine with the purpose to probe the influence of such substitutions on the hydrolysis profiles. Results show that for the unsubstituted complexes displacement of the labile chloride ligand by water requires that low energy barriers are surmounted for the aquation process to occur. Substitution with either the CF3 group in peripheral position or chloride with pyridine causes an increase of barriers heights. The only complex with an hydrolysis barrier comparable with that of cisplatin is the pyridine leaving ligand ruthenium complex.

U(IV) Aqueous Speciation from the Monomer to UO2 Nanoparticles: Two Levels of Control from Zwitterionic Glycine Ligands.

The fate of U(IV)O2 in the environment in a colloidal form and its dissolution and growth in controlled environments is influenced by organic ligation and redox processes, where both affect solubility, speciation, and transport. Here we investigate U(IV) aqueous speciation from pH 0 to 3 with the glycine (Gly) ligand, the smallest amino acid. We document evolution of the monomeric to the hexameric form from pH 0 to 3 via UV-vis spectroscopy and small-angle X-ray scattering (SAXS). Crystals of the hexamer [U6O4(OH)4(H2O)6(HGly)12]·12Cl-·12(H2O) (U6) were isolated at pH 2.15. The structure of U6 is a hexanuclear oxo/hydroxo cluster U6O4(OH)4 decorated by 12 glycine ligands and 6 water molecules. The effect of pH and temperature on U6 conversion to UO2 nanoparticles, or simply reversible aggregation, is detailed by transmission electron microscopy imaging, in addition to SAXS and UV-spectroscopy. Because of the zwitterion behavior of glycine, pH and temperature control over U(IV) speciation is complex. Unexpectedly, stability of the polynuclear cluster actually increases with increased pH. Speciation is sensitive to not only metal-oxo hydrolysis but also ligand lability and hydrophobic ligand-ligand interactions.

Insight into Electron-Donating Ancillary Ligands in Ruthenium Terpyridyl Complexes Configuration on Performances of Dye-Sensitized Solar Cells

Three heteroleptic ruthenium terpyridyl complexes, RC-T51, RC-T52, and RC-T53, with efficient electron-donating ancillary ligands were molecularly designed, synthesized and applied as sensitizers for dye-sensitized solar cell. With the replacement of labile isothiocyanates (NCS) ligand by electron-donating ancillary ligands, all the RC dyes exhibited superior optical properties and suitable electrochemical characteristics. The lowest excited-state decay dynamic analysis for RC dyes were carried out by time-resolved photoluminescence measurements. Among the RC dyes, the solar cell sensitized by RC-T53 achieved the best short-circuit current density of 14.20 mA cm–2 and power conversion efficiency of 6.17%. Compared with N749, DFT calculations, and transient absorbance decay kinetics rationalized the relatively inferior performances of RC dyes which were ascribed to the improper delocalization of the HOMO energy level and the inefficient dye generation process. Substituting the labile NCS ligand by electron...

Naked d-orbital in a centrochiral Ni(II) complex as a catalyst for asymmetric [3+2] cycloaddition

Chiral metal catalysts have been widely applied to asymmetric transformations. However, the electronic structure of the catalyst and how it contributes to the activation of the substrate is seldom investigated. Here, we report an empirical approach for providing insights into the catalytic activation process in the distorted Ni(II)-catalysed asymmetric [3+2] cycloaddition of α-ketoesters. We quantitatively characterize the bonding nature of the catalyst by means of electron density distribution analysis, showing that the distortion around the Ni(II) centre makes the dz2 orbital partially ‘naked’, wherein the labile acetate ligand is coordinated with electrostatic interaction. The electron-deficient dz2 orbital and the acetate act together to deprotonate the α-ketoester, generating the (Λ)-Ni(II)–enolate. The solid and solution state analyses, together with theoretical calculations, strongly link the electronic structure of the centrochiral octahedral Ni(II) complex and its catalytic activity, depicting a cooperative mechanism of enolate binding and outer sphere hydrogen-bonding activation.

Mechanistic Insights into the Rh-Catalyzed Transannulation of Pyridotriazole with Phenylacetylene and Benzonitrile: A DFT Study.

Computational studies were carried out to explore the mechanisms of Rh2(OAc)4-catalyzed transannulation of pyridotriazole with phenylacetylene and benzonitrile, respectively. For the Rh2(OAc)4-catalyzed divergent cyclization with phenylacetylene, the major product (cyclopropene derivative) might be formed via [2 + 2] cycloaddition to yield a metallacyclobutene intermediate followed by a reductive elimination pathway, where carboxylate ligand lability is considered to release a vacant equatorial site for the formation of Rh-carbenoid. The cyclopropenation of phenylacetylene via a commonly proposed [2 + 1] cycloaddition pathway, where the tetrabridged framework of Rh2(OAc)4 is preserved, however, might not play a dominant role. This is because the competing formal [2 + 3] pathway leading to the indolizine as a minor product is more likely to occur. The main factors responsible for the chemoselectivity in cyclization with phenylacetylene are discussed. For the Rh2(OAc)4-catalyzed transannulation of pyridotriazole with benzonitrile, a stepwise formal [2 + 3] pathway via a ylide intermediate is proposed regardless of whether the tetrabridged framework of Rh2(OAc)4 is preserved or not.

Double-Strand DNA Breaks Induced by Paracyclophane Gold(I) Complexes.

Gold(I) complexes of ClickPhos [2.2]paracyclophane ligands were synthesized in excellent yields and fully characterized by spectroscopic methods as well as X-ray crystallography. The complexes exhibit a rigid ligand backbone and a triazolyl moiety and were systematically studied with respect to their cytotoxic properties. In combination with the ionic complex [(GemPhos)Au(tht)][ClO4 ] (tht=tetrahydrothiophene), in which the gold(I) atom exhibits a distorted trigonal coordination sphere of two phosphines and a labile tht ligand, their efficiency in cytotoxicity was investigated in HeLa, MCF7, and HCT116 cells as well as in a zebrafish model. Their cytotoxicity and their mechanisms of action are different and involve apoptosis, necrosis, and DNA damage. The compounds presented herein are potent metal-based cytostatics displaying LD50 values from 3.5-38 μm in different tumor cell lines and induce double-strand DNA breaks (DSB) as shown by H2AX phosphorylation (γH2AX) at foci of DSBs.

Synthesis of new ruthenium(II) complexes derived from labile nitrile ligands: an alternative route to the preparation of trans-dichlorotetrakis(diphenylphosphine)ruthenium(II)

New ruthenium(II) complexes containing labile nitrile ligands have been prepared by treatment of either the polymer [{RuCl2(COD)}x] (COD = cycloocta-1,5-diene) (1) or its derivative [RuCl2(COD)(NCCH3)2]·NCCH3 (2) with the appropriate nitrile ligands in refluxing acetonitrile under argon. A new route to synthesis of trans-dichlorotetrakis(diphenylphosphine)ruthenium(II) (7) was also reported. A redetermination of the structure of 7 was undertaken and X-ray crystallographic data revealed that the complex crystallizes in the triclinic space group P-1 with unit cell dimensions a = 12.7016(9) Å, b = 13.0847(10) Å, c = 14.1498(10) Å, α = 101.46(3)°, V = 2080.6(3) Å3, Z = 2 and R = 0.0309. Its polymorph 7′ was also obtained. The crystal structure of 4 was also determined. This complex crystallizes in the monoclinic space group C2/c with unit cell dimensions a = 27.0510(3) Å, b = 11.0984(13) Å, c = 13.0450(16) Å, α = 90°, V = 3886.5(8) Å3, Z = 8 and R = 0.0282.

Synthesis and structural investigation of mono- and dimetallic N-heterocyclic carbene complexes of group VII transition metals

N-heterocyclic carbene complexes of group VII transition metals (Mn and Re) were synthesized and the electronic and structural aspects theoretically investigated. The synthesis yielded carbene complexes of type [Mx(CO)yL(NHC)] where M represents Mn or Re, x = 1, y = 4 and L = Cl, Br, I or M = Mn, x = 2, y = 9, L = CO. The synthesis of the mono- and dimetallic NHC complexes involved the substitution of labile carbonyl ligands for symmetrical and asymmetrical 1,3-disubstituted NHC ligands. Both aliphatic and aromatic N-substituent groups were incorporated into the heteroatomic, aromatic backbone of the imidazolylidene ligands. Coordination of the carbene ligand to the metal centre generated different results when comparing manganese NHC complexes to the rhenium NHC analogues. Analysis of the results indicated that only monometallic, halogenated NHC complex of Re could be synthesized and isolated, whereas the coordination of the imidazolium salts to Mn2(CO)10 produced axially substituted dimetallic carbene complexes. Spectroscopic (IR, NMR (1H and 13C) and structural (X-ray)) properties are reported and compared to those of other N-heterocyclic carbene derivatives. The structural features, coordination patterns and reactivity centres were examined to provide insight into the electronic and bonding environments of the metal-metal bond and the metal-NHC moiety.

Synthesis and electronic characterization of mixed diimine ligand rhodium(III) complexes using a versatile triflate precursor

We report here the first general, high purity, high yield synthesis of thirteen mixed diimine ligand complexes of rhodium(III), nine of which are new and four which are known and were made as controls. We utilized a bis–triflate intermediate because the more labile triflate ligands were easily displaced by incoming diimine ligands and allowed these syntheses to proceed in high yields (84–97%) under relatively mild reaction conditions. The purity of the products was determined by elemental analysis and 1H NMR. Electronic characterization was done on the compounds and we examined the effect of various electron donating and electron withdrawing substituents on the ground and excited state properties of the complexes. We observed that substitution on the 2,2′-bipyridine ligands causes only small changes in the redox potentials and the electronic spectra, while substitution on the 1,10-phenanthroline ligands causes more pronounced effects on the electronic properties, presumably due to the more rigid π system.

Dicarboxylato ligands in osmium carbonyl sawhorse clusters: Chelating vs. bridging

Seven new complexes comprising of diosmium(I) tetracarbonyl sawhorse units bound to dicarboxylate anions (DCAs) have been synthesized using microwave heating. Succinic, adipic, pimelic, suberic, tetradecanedioic, and terephthalic acids react with Os3(CO)12 at temperatures ranging from 180 to 205 °C for 12–20 min to produce the osmium sawhorse complexes, which are subsequently reacted with phosphine ligands to replace the labile axial CO ligands. X-ray crystallographic analysis was used to determine the molecular structures of these complexes. Two complexes, those with suberato and tetradecanedioato ligands, are dinuclear species containing Os2 sawhorse molecules with chelating DCAs that form intramolecular loops. The succinato, adipato and pimelato complexes are tetranuclear species consisting of two Os2 sawhorse moieties linked together by two bridging DCAs. Thus the straight-chain hydrocarbon backbone of the DCAs must contain at least six carbon atoms in order for these ligands to prefer to chelate a single Os2 unit instead of forming bridges between multiple Os2 units. The terephthalato complex is a triangular hexanuclear species consisting of a trimer of dimers with three bridging dicarboxylato anions.

β-SiH-Containing Tris(silazido) Rare-Earth Complexes as Homogeneous and Grafted Single-Site Catalyst Precursors for Hydroamination

A series of homoleptic rare-earth silazido compounds and their silica-grafted derivatives were prepared to compare spectroscopic and catalytic features under homogeneous and interfacial conditions. Trivalent tris(silazido) compounds Ln{N(SiHMe2)tBu}3 (Ln = Sc (1), Y (2), Lu (3)) are prepared in high yield by salt metathesis reactions. Solution-phase and solid-state characterization of 1–3 by NMR and IR spectroscopy and X-ray diffraction reveals Ln↼H–Si interactions. These features are retained in solvent-coordinated 2·Et2O, 2·THF, and 3·THF. The change in spectroscopic features characterizing the secondary interactions (νSiH, 1JSiH) from the unactivated SiH in the silazane HN(SiHMe2)tBu follows the trend 3 > 2 > 1 ≈ 2·Et2O > 2·THF ≈ 3·THF. Ligand lability follows the same pattern, with Et2O readily dissociating from 2·Et2O while THF is displaced only during surface grafting reactions. 1 and 2·THF graft onto mesoporous silica nanoparticles (MSN) to give Ln{N(SiHMe2)tBu}n@MSN (Ln = Sc (1@MSN), Y (2@MSN)) al...

Cobalt(II) chloride adducts with acetonitrile, propan-2-ol and tetrahydrofuran: considerations on nuclearity, reactivity and synthetic applications.

High-spin cobalt(II) complexes are considered useful building blocks for the synthesis of single-molecule magnets (SMM) because of their intrinsic magnetic anisotropy. In this work, three new cobalt(II) chloride adducts with labile ligands have been synthesized from anhydrous CoCl2, to be subsequently employed as starting materials for heterobimetallic compounds. The products were characterized by elemental, spectroscopic (EPR and FT-IR) and single-crystal X-ray diffraction analyses. trans-Tetrakis(acetonitrile-κN)bis(tetrahydrofuran-κO)cobalt(II) bis[(acetonitrile-κN)trichloridocobaltate(II)], [Co(C2H3N)4(C4H8O)2][CoCl3(C2H3N)]2, (1), comprises mononuclear ions and contains both acetonitrile and tetrahydrofuran (thf) ligands, The coordination polymer catena-poly[[tetrakis(propan-2-ol-κO)cobalt(II)]-μ-chlorido-[dichloridocobalt(II)]-μ-chlorido], [Co2Cl4(C3H8O)4], (2'), was prepared by direct reaction between anhydrous CoCl2 and propan-2-ol in an attempt to rationalize the formation of the CoCl2-alcohol adduct (2), probably CoCl2(HOiPr)m. The binuclear complex di-μ-chlorido-1:2κ4Cl:Cl-dichlorido-2κ2Cl-tetrakis(tetrahydrofuran-1κO)dicobalt(II), [Co2Cl4(C4H8O)4], (3), was obtained from (2) after recrystallization from tetrahydrofuran. All three products present cobalt(II) centres in both octahedral and tetrahedral environments, the former usually less distorted than the latter, regardless of the nature of the neutral ligand. Product (2') is stabilized by an intramolecular hydrogen-bond network that appears to favour a trans arrangement of the chloride ligands in the octahedral moiety; this differs from the cis disposition found in (3). The expected easy displacement of the bound solvent molecules from the metal coordination sphere makes the three compounds good candidates for suitable starting materials in a number of synthetic applications.

Cytotoxic Vanadium Complexes of Branched [ONNO]‐Type Diamine Bis(phenolato) Ligands

Vanadium complexes are attractive potential alternatives to platinum‐based anticancer drugs. Two vanadium(V) complexes, based on a common chelating tetradentate diaminobis(phenolato) ligand featuring a branched connectivity but differing in their labile ligands, were synthesized and characterized. Whereas the isopropoxido complex was obtained as a mixture of cis and trans isomers with regard to the orientation of the labile group vs. the amine sidearm, the salicylato‐containing complex was obtained as a single trans isomer. X‐ray structures of the complexes featured octahedral geometry for both. The two complexes exhibited high cytotoxic activity toward different cancer cells, often higher than that of cisplatin, including toward cisplatin‐resistant ovarian cancer cells. These complexes demonstrated rapid hydrolysis, releasing the labile ligand within several minutes, with no indications of release of free chelating ligand after water exposure, suggesting that polynuclear hydrolysis products are involved in the cellular activity.

Selective Synthesis of Cyclic Carbonate by Salalen-Aluminum Complexes and Mechanistic Studies.

Salalen-aluminum complexes were synthesized and used as catalysts in the reactions of CO2 with different epoxides. The reaction of cyclohexene oxide and CO2 was thoroughly investigated. In particular, the effect of the reaction conditions (nature and equivalents of the co-catalyst, CO2 pressure, and temperature) and of the ligands (substituents on the ancillary ligand, nature of the labile ligand, and nature of the nitrogen-donor atoms) on the results of this reaction was studied. The cycloaddition reaction of CO2 with terminal epoxides bearing different functional groups was realized. Moreover, NMR mechanistic studies provided information on the catalytic cycle. Interestingly, the characterization of an intermediate species in the mechanism of the reaction of cyclohexene oxide with CO2 , catalyzed by one of the salalen-aluminum complexes, was accomplished.

Anilinopyridinate-supported Ru2x+ (x = 5 or 6) paddlewheel complexes with labile axial ligands.

Five new metal-metal bonded Ru2 compounds are presented and discussed: Ru2(ap)4ONO2 (2), [Ru2(ap)4NCMe][BF4] (3), Ru2(ap)4FBF3 (4), Ru2(ap)4OTf (5), and [Ru2(ap)4OTf][Ag(OTf)2] (6) (ap = 2-anilinopyridinate). All compounds have a (4,0) arrangement of the ap ligands about the Ru-Ru bond and contain one sterically blocked axial site and one site containing a labile ligand. These compounds display some of the shortest Ru-Ru distances known for this class of compounds. We demonstrate a reversible interconversion between compounds 3 and 4 as the MeCN and BF4- ligands are readily displaced. Despite the presence of labile axial ligands, compounds 2-5 remain high spin with an S = 3/2 ground state as determined by EPR spectroscopy.

Mixed Ligated Tris(amidinate)dimolybdenum Complexes as Catalysts for Radical Addition of CCl4 to 1-Hexene: Leaving Ligand Lability Controls Catalyst Activity.

We synthesized a series of mixed ligated tris(amidinate)dimolybdenum complexes, namely, [Mo2(DAniF)3(L)] [DAniF = N,N'-di(p-anisyl)formamidinate; L = acetate (OAc; 1a), m-diphenylphosphino benzoate (m-PPh2Bz; 1b), nicotinate (Nico; 1c), benzoate (Bz; 1d), 3-furoate (3-Furo; 1e), isonicotinate (IsoNico; 1f), and trifluoromethanesulfonate (OTf; 1g)], which served as catalysts for radical addition of CCl4 to 1-hexene to give 1,1,1,3-tetrachloroheptane. These mixed ligated complexes 1a-g afforded the higher yield of the radical addition product than a homoleptic DAniF complex, [Mo2(DAniF)4] (2). Among them, complexes 1a and 1g gave the radical addition product quantitatively after 9 h with a short induction period. When complexes 1a and 1g were treated with CCl4, we detected the mixed-valence Mo2(II/III) complex, [Mo2(DAniF)3Cl2] (4), in electrospray ionization mass spectrometry measurements, indicating that the leaving nature of the L ligands was a crucial factor for initiating the catalytic reaction: the catalytic activity of the carboxylate-bridged complex 1a and the triflate-bridged complex 1g in the initial 30 min highly depended on the ligand-exchange rate of L, as estimated by monitoring the reaction with CCl4 in pyridine, giving the pyridine adduct complex, [Mo2(DAniF)3Cl(py)] (3).

Robust, Transformable, and Crystalline Single-Node Organometallic Networks Constructed from Ditopic m-Terphenyl Isocyanides.

The preparation of 3D and 2D Cu(I) coordination networks using ditopic m-terphenyl isocyanides is described. The incorporation of sterically encumbering substituents enables the controlled, solid-state preparation of Cu(I) tris-isocyanide nodes with a labile solvent ligand in a manner mirroring solution-phase chemistry of monomeric complexes. The protection afforded by the m-terphenyl groups is also shown to engender significant stability towards heat as well as acidic or basic conditions, resulting in robust single-metal-node networks that can transition from 3D to 2D extended structures.