Cadmium Complexes—A Novel Family in the Coordination Chemistry of 1,2-bis(arylimino)acenaphthenes
, Veronika I. Komlyagina 1, Saltanat Appazova 3, Banu Diyarova 4,*, Klara Darmagambet 3, Nurbol Appazov 3, Nikolai F. Romashev 1 and Artem L. Gushchin 1,*Round 1
Reviewer 1 Report
Comments and Suggestions for AuthorsThe manuscript titled "Cadmium complexes – a novel family in the coordination 2 chemistry of 1,2-bis(arylimino)acenaphthenes". However, I cannot recommend the manuscript for acceptance in its present state. The following technical suggestions will greatly improve, in my opinion, the value of the submitted work:
- There are only .cif files and the .pdf files of checkcif. The supplementary file including figures and tables is absent.
- Line 48 to 49, the introduction of mercury complexes is too simple and sudden.
- According to the literature, the dimeric centrosymmetric Ni(II) and Zn(II) complexesexhibited distorted square-pyramidal and trigonal bipyramidal environment. In this article, why the Cd2+ in compound 1 shows a square-pyramidal environment, while the Cd2+ in 2 and 3 have trigonal bipyramidal one?
- As the solvents and the hydrogen atoms are omitted, the label of Figure 1 should be revised.
- The paper needs to be improved carefully for its English.For example, line 18, “lad to”; line 142, “Finding the minimum point”; line 39, “d-elements”.
Author Response
The manuscript titled "Cadmium complexes – a novel family in the coordination 2 chemistry of 1,2-bis(arylimino)acenaphthenes". However, I cannot recommend the manuscript for acceptance in its present state. The following technical suggestions will greatly improve, in my opinion, the value of the submitted work:
We are grateful to the Referee #1 for the positive evaluation of our work. Please find our responses below.
- There are only .cif files and the .pdf files of checkcif. The supplementary file including figures and tables is absent.
Answer: Unfortunately, due to technical reasons, the document with supporting information was lost. Please find the attached document.
- Line 48 to 49, the introduction of mercury complexes is too simple and sudden.
Answer: We agree with the Referee regarding this comment. The corresponding changes has been made to the article.
- According to the literature, the dimeric centrosymmetric Ni(II) and Zn(II) complexes exhibited distorted square-pyramidal and trigonal bipyramidal environment. In this article, why the Cd2+ in compound 1 shows a square-pyramidal environment, while the Cd2+ in 2 and 3 have trigonal bipyramidal one?
Answer: By way of comparison with zinc(II) and nickel(II) complexes, the aim was to demonstrate the potential for a range of geometries of the coordination polyhedra of such complexes. Minor alterations in the ligand structure, in conjunction with subtle changes in the composition of the coordination sphere, can exert a substantial influence on the final geometry of the complex.
The geometry of complexes 1, 2 and 3 is distinguished by their distinct coordination numbers. Specifically, complex 1 exhibits a coordination number (CN) of 5 (distorted square-pyramidal geometry), while complexes 2 and 3 demonstrate a coordination number of 6 (octahedral geometry). Apparently, the coordination of an additional water molecule to the Cd2+ ion is not energetically favorable.
- As the solvents and the hydrogen atoms are omitted, the label of Figure 1 should be revised.
Answer: Apparently this comment concerns Figure 2. The corresponding corrections have been made.
- The paper needs to be improved carefully for its English. For example, line 18, “lad to”; line 142, “Finding the minimum point”; line 39, “d-elements”.
Answer: We are grateful to the Referee for this comment. Inaccuracies in the English have been corrected throughout the text.
Author Response File: 
Author Response.pdf
Reviewer 2 Report
Comments and Suggestions for AuthorsThe work entitled "Cadmium complexes – a novel family in the coordination chemistry of 1,2-bis(arylimino)acenaphthenes" by B. Diyarova, N. F. Romashevet, Artem L. Gushchin et al. presents the synthesis and characterization of three new cadmium complexes based on 1,2-bis[(2,4,6-trimethyl-phenyl)imino]acenatephene (tmp-bian) ligand. Bis(imino)acenaphthenes began to be used as non-innocent ligands in coordination chemistry around two decades ago and the authors complete the picture with the cadmium complexes.
The tmp-bian cadmium complexes were characterized by spectral (IR and NMR), structural measurements (X-ray diffraction) and their electrochemical properties by cyclic voltammetry (only 1 and3). Please add a comment for the reasons of not including the compound 2 in CV measurements, even if it was specified that compound 2 is obtained in a mixture with compound 3.
In the Figure 4 are represented the frontier molecular orbitals. Please change the order of HOMO and LUMO (upper side).
Please reformulate or explain the fragment “The presence of two closely located reduction peaks in the cyclic voltammogram of complex 3 correlates with the presence of two tmp-bian ligands in its structure. For complex 1, these peaks seem to merge into one broad cathodic peak.” Both complexes have two tmp-bian ligands in their structure.
The novelty is slightly reduced, because this work continues the previous works published by the authors, but is well organized and conducted. The references are related with the comments. The paper contained experimental work, and the data are corroborated. The manuscript can be accepted after minor corrections.
Author Response
The work entitled "Cadmium complexes – a novel family in the coordination chemistry of 1,2-bis(arylimino)acenaphthenes" by B. Diyarova, N. F. Romashevet, Artem L. Gushchin et al. presents the synthesis and characterization of three new cadmium complexes based on 1,2-bis[(2,4,6-trimethyl-phenyl)imino]acenatephene (tmp-bian) ligand. Bis(imino)acenaphthenes began to be used as non-innocent ligands in coordination chemistry around two decades ago and the authors complete the picture with the cadmium complexes.
The tmp-bian cadmium complexes were characterized by spectral (IR and NMR), structural measurements (X-ray diffraction) and their electrochemical properties by cyclic voltammetry (only 1 and3). Please add a comment for the reasons of not including the compound 2 in CV measurements, even if it was specified that compound 2 is obtained in a mixture with compound 3.
Answer: Unfortunately, the cyclic voltammogram of complex 2 could not be recorded due to difficulties in isolating it individually. The corresponding addition has been inserted to the main text of the manuscript.
In the Figure 4 are represented the frontier molecular orbitals. Please change the order of HOMO and LUMO (upper side).
Answer: Corrected
Please reformulate or explain the fragment “The presence of two closely located reduction peaks in the cyclic voltammogram of complex 3 correlates with the presence of two tmp-bian ligands in its structure. For complex 1, these peaks seem to merge into one broad cathodic peak.” Both complexes have two tmp-bian ligands in their structure.
Answer: In our opinion, the differences in the reduction behavior of complexes 1 and 3 can be related to their structural differences. In complex 1, two tmp-bian ligands are coordinated to different cadmium atoms, whereas in complex 3, both ligands are bound to the same cadmium center. The corresponding changes have been made to the article.
The novelty is slightly reduced, because this work continues the previous works published by the authors, but is well organized and conducted. The references are related with the comments. The paper contained experimental work, and the data are corroborated. The manuscript can be accepted after minor corrections.
Answer: We are grateful to the Referee #2 for the positive evaluation of our work.
Author Response File: Author Response.pdf
Round 2
Reviewer 1 Report
Comments and Suggestions for AuthorsThe revised article can be accepted.
