Synthesis, Spectroscopic Studies and X-Ray Crystal Structure Analysis of Cobalt Nitroprusside, Co[Fe(CN)<sub>5</sub>NO]·5H<sub>2</sub>O

Mullica, D. F.; Tippin, Douglas; Sappenfield, E. L.

doi:10.1080/00958979109409738

Cited by 36 publications

(50 citation statements)

References 21 publications

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“…No significant changes are observed in the values of δ and ∆ for the iron cation within the complex anion on water removal ( Figure 4 and Table 2). This means that while the temperature remains within the stability range for these materials (on average, below 160°C), the [Fe(CN) 5 NO] structural unit is not affected by the heating process. The exception in this behavior is observed for orthorhombic (Amm2) copper nitroprusside, which undergoes a phase transformation on dehydration.…”

Section: Resultsmentioning

confidence: 95%

“…This is observed in its bond angle with the equatorial CN ligands, N eq -Cu-N′ eq , which is 171°. 20 Since the axial cyanide ligand of [Fe(CN) 5 NO], which remains unlinked at N end, and the water molecules in [Cu(NC) 4 (H 2 O) 2 ] adopt a parallel arrangement, the resulting structure appears as a sequence of rippled layers (Figure 2a). Within the crystal these layers are kept together by the Van der Waals forces.…”

Section: Resultsmentioning

confidence: 98%

“…In this cubic array of [Fe(CN) 5 NO] blocks, the vacancy of the outer metal is related to the existence of unbridged NO ligands at the O end. In the Fm3m structure, six molecular blocks [Fe-(CN) 5 NO] are arranged in such a way that their six unbridged NO groups are oriented toward the center of a cube forming a second cavity (the nitrosyl bound cage) with a diameter of ca. 5 Å (Figure 3).…”

Section: Resultsmentioning

confidence: 99%

“…In all these structures the iron atom is coordinated to five C atoms of CN ligands and to the N atom of the NO group. The resulting octahedron, [Fe(CN) 5 NO], is distorted due to the large electron withdrawing effect (π-back-bonding) of the nitrosyl group (NO) with respect to the cyanide ligand. The NO group has a lowenergy π*-antibonding orbital which is partially populated by the t 2g electrons from the iron atom strengthening the ON-Fe bond.…”

Section: Resultsmentioning

confidence: 99%

“…Mössbauer parameters (δ and ∆) of iron in the structural unit [Fe(CN) 5 NO] are practically independent of the outer metal and of the crystal structure adopted by a given composition ( Table 2). The strongly bonded CN and NO ligands effectively shield the iron atom from changes in the outer environment.…”

Section: Resultsmentioning

confidence: 99%

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On the Microporous Nature of Transition Metal Nitroprussides

et al. 2003

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Nitroprussides of divalent transition metals form a family of microporous molecular materials. Their properties in this sense depend on the transition metal cation involved and also on the preparative method, which determine their crystal structures. The stable phases of this family of materials belong to one of the following crystal structures: orthorhombic (Pnma) (Mn 2+ , Fe 2+ , Cu 2+ , Zn 2+ , and Cd 2+ ), cubic (Fm3m) (Co 2+ and Ni 2+ ), and orthorhombic (Amm2) (Cu 2+ ). These materials are stable up to above 160°C, while their dehydration takes place around 100°C. On dehydration, Amm2 copper complex changes into a tetragonal (I4mm) phase. The microporous nature of these materials is discussed according to their crystal structure and correlating structural and adsorption data. The accessibility to the pore system was evaluated through adsorption of H 2 O, CO 2 , and N 2 . Pores of both orthorhombic and cubic structures are accessible to H 2 O and CO 2 in experiments carried out at 23 and 0°C, respectively; however, they are inaccessible to N 2 at -196°C. This behavior is discussed as related to the large polarizing power of the nitrosyl (NO) ligand which distorts the local environment of the iron atom and reduces the effective window cross section. The small pores of tetragonal copper nitroprusside were inaccessible to the adsorbates used.

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Section: Resultsmentioning

confidence: 95%

Section: Resultsmentioning

confidence: 98%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

Section: Resultsmentioning

confidence: 99%

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On the Microporous Nature of Transition Metal Nitroprussides

et al. 2003

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Deciphering Ligand Controlled Structural Evolution of Prussian Blue Analogues and Their Electrochemical Activation during Alkaline Water Oxidation

et al. 2022

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Herein, we have demonstrated the control over the structure of precatalysts to tune the properties of the active catalysts and their water oxidation activity. The reaction of K 3 [Fe(CN) 6 ] and Na 2 [Fe(CN) 5 (NO)] with Co(OH) 2 @CC produced precatalysts PC-1 and PC-2, respectively, with distinct structural and electronic features. The replacement of the À CN group with strong π-acceptor À NO modulates the electronic and atomic structure of PC-2. As a result, a facile electrochemical transformation of PC-2 into active catalyst FeÀ Co-(OH) 2 -Co(O)OH (AC-2) has been attained only in 15 CV cycles while 600 CV cycles are required for the electrochemical activation of PC-1 into AC-1. The X-ray absorption studies reveal the contraction of the CoÀ O and FeÀ O bond in AC-2 because of the presence of a higher amount of Co 3 + and Fe 3 + than in AC-1. The high valent Co 3 + and Fe 3 + modulates the electronic properties of AC-2 and assists in the OÀ O bond formation, leading to the improved water oxidation activity.

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Deciphering Ligand Controlled Structural Evolution of Prussian Blue Analogues and Their Electrochemical Activation during Alkaline Water Oxidation

et al. 2022

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Synthesis, Spectroscopic Studies and X-Ray Crystal Structure Analysis of Cobalt Nitroprusside, Co[Fe(CN)₅NO]·5H₂O

Cited by 36 publications

References 21 publications

On the Microporous Nature of Transition Metal Nitroprussides

On the Microporous Nature of Transition Metal Nitroprussides

Deciphering Ligand Controlled Structural Evolution of Prussian Blue Analogues and Their Electrochemical Activation during Alkaline Water Oxidation

Deciphering Ligand Controlled Structural Evolution of Prussian Blue Analogues and Their Electrochemical Activation during Alkaline Water Oxidation

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Synthesis, Spectroscopic Studies and X-Ray Crystal Structure Analysis of Cobalt Nitroprusside, Co[Fe(CN)5NO]·5H2O

Cited by 36 publications

References 21 publications

On the Microporous Nature of Transition Metal Nitroprussides

On the Microporous Nature of Transition Metal Nitroprussides

Deciphering Ligand Controlled Structural Evolution of Prussian Blue Analogues and Their Electrochemical Activation during Alkaline Water Oxidation

Deciphering Ligand Controlled Structural Evolution of Prussian Blue Analogues and Their Electrochemical Activation during Alkaline Water Oxidation

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Synthesis, Spectroscopic Studies and X-Ray Crystal Structure Analysis of Cobalt Nitroprusside, Co[Fe(CN)₅NO]·5H₂O