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Unexpected Formation and Structural Characterization of a Dinuclear Sodium Half-Sandwich Complex

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Unexpected Formation and Structural Characterization of a Dinuclear Sodium Half-Sandwich Complex inorganics Article Unexpected Formation and Structural Characterization of a Dinuclear Sodium Half-Sandwich Complex Nicole Harmgarth 1, Phil Liebing 2 ID , Liane Hilfert 1 ID , Sabine Busse 1 and Frank T. Edelmann 1,* 1 Chemisches Institut der Otto-von-Guericke-Universität Magdeburg, 39106 Magdeburg, Germany; [email protected] (N.H.); [email protected] (L.H.); [email protected] (S.B.) 2 ETH Zürich, Laboratorium für Anorganische Chemie, Vladimir-Prelog-Weg 2, 8093 Zürich, Switzerland; [email protected] * Correspondence: [email protected]; Tel.: +49-391-67-58327; Fax: +49-391-67-42933 Received: 12 April 2018; Accepted: 7 May 2018; Published: 9 May 2018 Abstract: Treatment of N,N0-diisopropylcarbodiimide with sodium cyclopentadienide (NaCp) in a molar ratio of 1:1 in THF solution resulted in formation of the unexpected dinuclear i i sodium half-sandwich complex [NaC5H3{C(NH Pr)(=N Pr)}2-1,2]2 (1) as colorless crystals in low yield. The newly formed ligand, which belongs to the group of 6-aminofulvene-2-aldiminate ligands, coordinates to sodium in an h5-coordination mode via the cyclopentadienyl ring. Dimerization occurs through additional chelating kN,N0-coordination of the amidine substituents. The NMR data of 1 indicated a slow dimer/monomer equilibrium in solution. A serendipitously i i i isolated hydrolysis product,{m-( PrNH)2C=O}2[NaC5H3{C(NH Pr)(=N Pr)}2-1,2]2 (2), contains the new 6-aminofulvene-2-aldiminate ligand in the N,N0-chelating coordination mode with the cyclopentadiene ring being uncoordinated. In this case, dimerization occurs through the presence of two bridging neutral N,N0-diisopropylurea ligands. Both compounds have been structurally characterized by single-crystal X-ray diffraction. Keywords: Sodium; amidinate ligand; cyclopentadienyl; aminofulvene-aldiminate; crystal structure 1. Introduction 0 0 − N,N -Chelating anionic ligands—such as the amidinates, [RC(NR )2] , and guanidinates, 0 − [R2NC(NR )2] (Scheme1)—have become indispensable in various fields of organometallic and coordination chemistry [1–9]. These ligands form well-defined complexes with virtually every metallic element in the periodic system. In main group metal chemistry, bulky amidinate and guanidinate ligands have been successfully employed to stabilize low coordination numbers and uncommon oxidation states [10–12]. Numerous transition metal amidinate and guanidinate complexes have been demonstrated to exhibit high catalytic activity in a variety of organic transformations [2,13–16]. Moreover, alkyl-substituted amidinate and guanidinate complexes of various metals have been established as ALD (atomic layer deposition) and MOCVD (metal–organic chemical vapor deposition) precursors for the deposition of thin films of useful materials, such as metals, metal oxides or metal nitrides, among others [17–19]. Inorganics 2018, 6, 47; doi:10.3390/inorganics6020047 www.mdpi.com/journal/inorganics Inorganics 2018, 6, 47 2 of 9 Inorganics 2018, 6, x FOR PEER REVIEW 2 of 9 Inorganics 2018, 6, x FOR PEER REVIEW 2 of 9 . SchemeScheme 1. Schematic representation of amidinate anions (a) and guanidinate anions (b). Scheme 1. Schematic representation of amidinate anions (a)) andand guanidinateguanidinate anionsanions ((b).). Making the amidinate and guanidinate ligands extremely versatile, the substituents at all three Making the the amidinate amidinate and and guanidinate guanidinate ligands ligands extr extremelyemely versatile, versatile, the substituents the substituents at all atthree all atoms of the N–C–N backbone can be varied. A generally applicable synthetic route to lithium threeatoms atomsof the ofN–C–N the N–C–N backbone backbone can be can varied. be varied. A generally A generally applicable applicable synthetic synthetic route to routelithium to amidinate precursors involves the addition of organolithium reagents to N,N′-disubstituted lithiumamidinate amidinate precursors precursors involves involves the addition the addition of oforganolithium organolithium reagents reagents to to NN,,NN0′-disubstituted-disubstituted carbodiimides, as shown in Scheme 2. The substituents R and R′ can be varied in a wide range and, carbodiimides, as as shown shown in in Scheme Scheme 2.2. The The substituents substituents R Rand and R′ Rcan0 canbe varied be varied in a inwide a wide range range and, consequently, a large library of amidinate ligands has become available [1–9]. Closely related and,consequently, consequently, a large a large library library of ofamidinate amidinate ligands ligands has has become become available available [1–9]. [1–9]. Closely Closely related guanidinate anions can be accessed in a similarly manner by adding lithium diorganoamides, LiNR2, guanidinate anions can be accessed in a similarly manner by adding lithium diorganoamides, LiNR2,, to carbodiimides. 2 to carbodiimides. Scheme 2. General synthetic route to lithium amidinates. Scheme 2. General synthetic route to lithium amidinates. At the outset of the present study, we wondered if it might be possible to directly attach a At the outset of the present study, we wondered if it might be possible to directly attach a cyclopentadienylAt the outset ring of theto the present amidinate study, N–C–N we wondered backbone if by it mightthe use be of possible sodium tocyclopentadienide, directly attach a cyclopentadienyl ring to the amidinate N–C–N backbone by the use of sodium cyclopentadienide, NaCp,cyclopentadienyl as a nucleophile. ring to the We amidinate now report N–C–N the backbone outcome by of the this use ofreaction sodium and cyclopentadienide, the structural NaCp, as a nucleophile. We now report the outcome of this reaction and the structural characterizationNaCp, as a nucleophile. of the unexpected We now report product. the outcome of this reaction and the structural characterization characterization of the unexpected product. of the unexpected product. 2. Results and Discussion 2. Results and Discussion 2. Results and Discussion The reaction of 1 equiv. of sodium cyclopentadienide, NaCp, with The reaction of 1 equiv. of sodium cyclopentadienide, NaCp, with N,N′-diisopropylcarbodiimideThe reaction of 1 equiv. of was sodium carried cyclopentadienide, out in THF solution NaCp, at with roomN ,temperatureN0-diisopropylcarbodiimide and resulted in N,N′-diisopropylcarbodiimide was carried out in THF solution at room temperature and resulted in formationwas carried of out a inclear, THF light-brown solution at roomsolution. temperature Remova andl of resultedthe solvent, in formation followed of by a clear, extraction light-brown with formation of a clear, light-brown solution. Removal of the solvent, followed by extraction with nsolution.-pentane, Removal provided of thea yellow solvent, solution followed besides by extraction a large withamountn-pentane, of insoluble provided brown a yellow material. solution All n-pentane, provided a yellow solution besides a large amount of insoluble brown material. All attemptsbesides ato large crystallize amount the of latter insoluble from browndiethyl material.ether or THF All failed. attempts Crystallization to crystallize of the the lattern-pentane from attempts to crystallize the latter from diethyl ether or THF failed. Crystallization of the n-pentane filtratediethyl at ether 4 °C orafforded THF failed. colorless, Crystallization needle-like crys of thetals nin-pentane low yield. filtrate An IR at spectrum 4 ◦C afforded of the colorless, product filtrate at 4 °C afforded colorless, needle-like crystals in low yield. An IR spectrum of the product suggestedneedle-like that crystals the expected in low simple yield. addition An IR spectrum reaction (Scheme of the product 3a) had suggestednot taken place, that theas it expected showed suggested that the expected simple addition reaction (Scheme 3a) had not taken place, as it showed threesimple bands addition typical reaction for NH (Scheme functional3a) groups had not at ν taken 3436 place,m (νas NH), as it 3386 showed m (ν threes NH),bands 3223 m typical (νs NH). for A three bands typical for NH functional groups at ν 3436 m (νas NH), 3386 m (νs NH), 3223 m (νs NH). A single-crystalNH functional X-ray groups diffraction at n 3436 mstudy (nas NH),revealed 3386 the m (nformations NH), 3223 of man ( nunexpecteds NH). A single-crystal dimeric sodium X-ray single-crystal X-ray diffraction study revealed the formation of an unexpected dimeric sodium half-sandwichdiffraction study complex revealed [NaC the formation5H3{C(NHiPr)(=N of an unexpectediPr)}2-1,2]2 ( dimeric1). As sodiumillustrated half-sandwich in Scheme complex3b, the 5 3 i i 2 2 half-sandwich complexi i [NaC H {C(NH Pr)(=N Pr)} -1,2] (1).i As illustratedi − in Scheme 3b, the bis(amidino)-substituted[NaC5H3{C(NH Pr)(=N Pr)} cyclopentadienyl2-1,2]2 (1). As anion illustrated [C5H3{C(NH in SchemePr)(=N3b,Pr)} the2-1,2] bis(amidino)-substituted had formed through i i − bis(amidino)-substituted cyclopentadienyli anioni [C5H3{C(NH− Pr)(=N Pr)}2-1,2] had formed through doublecyclopentadienyl addition of anion N,N [C′-diisopropylcarbodiimide5H3{C(NH Pr)(=N Pr)}2-1,2] to thehad cyclopentadienyl formed through ring. double With addition ca. 9% of double addition of N,N′-diisopropylcarbodiimide to the cyclopentadienyl ring. With ca. 9% (determinedN,N0-diisopropylcarbodiimide after the crystal structure to the cyclopentadienyl had been elucidated) ring. Withthe isolated ca. 9% (determinedyield of 1 was after reproducibly the crystal (determined after the crystal structure had been elucidated) the isolated
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